CN108455650A - A kind of preparation method of anhydrous samarium trichloride - Google Patents
A kind of preparation method of anhydrous samarium trichloride Download PDFInfo
- Publication number
- CN108455650A CN108455650A CN201810394683.1A CN201810394683A CN108455650A CN 108455650 A CN108455650 A CN 108455650A CN 201810394683 A CN201810394683 A CN 201810394683A CN 108455650 A CN108455650 A CN 108455650A
- Authority
- CN
- China
- Prior art keywords
- reaction
- samarium
- ammonium chloride
- mesh
- anhydrous
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/253—Halides
- C01F17/271—Chlorides
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of preparation methods of anhydrous samarium trichloride, and the preparation method is reacted using samarium oxide as raw material using chloride solid, then is passed through dry hydrogen chloride gas, are heated to that the reaction was complete, and product is dried, anhydrous samarium trichloride is obtained.Ammonium chloride and hydrogen chloride gas is used in combination, and combination matching reactant dosage, so that ammonium chloride and hydrogen chloride is acted synergistically, adjusts each reactant position relationship, keep reaction more abundant, reaction product yield is high, decompression drying under inert atmosphere prevents the generation of redox side reaction, improves product purity, safe production process is effective, products pure.
Description
Technical field
The invention belongs to rare earth material preparation fields, relate generally to a kind of preparation method of anhydrous rare-earth chlorination samarium.
Background technology
Rare earth element is the general name of IIIB races yttrium and lanthanide series in periodic table, is active metal, property extremely phase
Seemingly, there is important bioactivity and pharmacotoxicological effect, two kinds of salt systems of chloride and fluoride can be used.Anhydrous rare-earth chlorination is
Prepare the basic agent of rear earth containing organic compound.
The method for preparing anhydrous rare earth chloride at present can pass through gold by tetrahydrofuran complex method in THF solution
Belong to exchange reaction and prepare anhydrous rare earth chloride, from rare earth metal through being reacted with mercury chloride, prepares anhydrous rare-earth chlorination
THF complexs, but reaction is related to poisonous and harmful substance, is unfavorable for industrialized production；Ammonium chloride sublimed method is to turn rare earth oxide
Rare earth chloride is turned to, but with the generation of redox side reaction in reaction process, it is difficult to obtain the higher anhydrous chlorination of purity
Rare earth；Anhydrous rare earth chloride prepared by rare earth oxide chloridising is easy residual impurity and water-insoluble, and chlorination temperature requires height,
Complex process.The water imbibition of water water samarium trichloride is very strong, and redox reaction easily occurs and generates samarium oxychloride, influences industry and answers
With.
The new preparation process of anhydrous rare-earth chlorination from rare earth oxide prepare anhydrous rare-earth chlorination (Ding Zongbiao,
Cheng Kejun, chemical journal, 1997,55:It 1004-1008) discloses a kind of using trim,ethylchlorosilane as deicer preparation nothing
The method of water rare earth chloride is reacted in room temperature, THF and is carried out under a dry nitrogen atmosphere, methanol and trim,ethylchlorosilane mistake
Amount, reaction stop after 15 hours, and thin crystalline white solid is precipitated, and continuation is heated to reflux 3h, decompression removal volatilization under nitrogen flowing
Property substance, product washs through dry pentane, and it is target product that vacuum drying, which obtains white solid, although the method condition temperature
With, but program is complicated, is related to toxic harmful reagent, is unsuitable for industrial production.CN107827140A discloses a kind of anhydrous rare earth chlorine
Seven water rare earth-iron-borons point are carried out fluidisation dehydration for three sections by the preparation method of compound, and dehydration carries out under hydrogen chloride gas atmosphere,
The dewatering need to pass through three vulcanizations and be dehydrated, and need strict temperature control and wind speed, be not suitable for industrial production.
Samarium trichloride can be used to prepare samarium metal, it is also possible to make the fluxing agent of sodium chloride and calcium chloride, or for preparing samarium
Organo-metallic compound, therefore it provides a kind of safe and effective, products pure, the method for preparing anhydrous samarium trichloride easy to operate
It is of great significance and bright prospects.
Invention content
In view of the deficiencies of the prior art and actual demand, the present invention provide a kind of preparation method of anhydrous samarium trichloride, high
Effect prepares anhydrous samarium trichloride, and easy to operate, raw material is easy to get.
For this purpose, the present invention uses following technical scheme：
In a first aspect, the present invention provides a kind of preparation method of anhydrous samarium trichloride uses ammonium chloride using samarium oxide as raw material
Solid is reacted, then is passed through dry hydrogen chloride gas, is heated to that the reaction was complete, and product is dried, anhydrous samarium trichloride is obtained.
In the present invention, using samarium oxide as raw material, ammonium chloride and dry hydrogen chloride gas is used in combination, makes hydrogen chloride gas
Not only it had served as chlorinating agent but also had served as protective atmosphere, and determined the best opportunity that hydrogen chloride gas is passed through so that chloride solid and chlorination
Hydrogen acts synergistically, and keeps samarium oxide reaction more abundant, improves efficiency of pcr product, and by decompression drying, high degree reduces production
The water content of object obtains pure anhydrous samarium trichloride, reduces the hydrolysis of samarium trichloride.
Preferably, the method further includes pretreated step.
Preferably, the pretreatment specifically includes：The samarium oxide and ammonium chloride are pulverized and sieved.
Preferably, the mesh number of samarium oxide sieving is 100-160 mesh, for example, can be 100 mesh, 105 mesh, 110 mesh,
115 mesh, 120 mesh, 125 mesh, 130 mesh, 135 mesh, 140 mesh, 145 mesh, 150 mesh, 155 mesh or 160 mesh, preferably 120-140 mesh.
Preferably, the mesh number of ammonium chloride sieving is 100-150 mesh, for example, can be 100 mesh, 105 mesh, 110 mesh,
115 mesh, 120 mesh, 125 mesh, 130 mesh, 135 mesh, 140 mesh, 145 mesh or 150 mesh.
It is a discovery of the invention that the samarium oxide and ammonium chloride after pulverizing and sieving can improve reaction efficiency, keep reactant abundant
Reaction, and under the grit number range excessively, best results.
Preferably, the chloride solid is laid in reaction unit bottom, and samarium oxide is laid on chloride solid.
It is a discovery of the invention that can make reactant branch evenly by the way of tiling, reaction is more abundant.
Preferably, the mass ratio of the samarium oxide and ammonium chloride is 1:(1-3), such as can be 1:1、1:1.2、1:1.3、
1:1.4、1:1.5、1:1.6、1:1.8、1:2、1:2.2、1:2.5、1:2.6、1:2.8 or 1:3, preferably 1:2.
Preferably, ammonium chloride tiling thickness is 5-15cm, for example, can be 5cm, 6cm, 7cm, 8cm, 9cm, 10cm,
11cm, 12cm, 13cm, 14cm or 15cm, preferably 8cm.
It is a discovery of the invention that in the mass ratio of the samarium oxide and ammonium chloride, and in the range of ammonium chloride tiling thickness
Interior reaction is more stablized abundant.
Preferably, the heating is by the way of gradient increased temperature.
Preferably, the rate of the heating be 10-20 DEG C/min, such as can be 10 DEG C/min, 11 DEG C/min, 12 DEG C/
Min, 13 DEG C/min, 14 DEG C/min, 15 DEG C/min, 16 DEG C/min, 17 DEG C/min, 18 DEG C/min, 19 DEG C/min or 20 DEG C/min.
It is a discovery of the invention that the gradient increased temperature and heating rate is within the scope of 10-20 DEG C/min, temperature of charge is distributed more
Add uniformly, avoid local temperature excessively high, reaction carries out gentler.
Preferably, described to carry out isothermal reaction when being warming up to 305-360 DEG C, for example, can be 305 DEG C, 308 DEG C, 310 DEG C,
315℃、318℃、320℃、322℃、325℃、328℃、330℃、335℃、340℃、345℃、350℃、355℃、358℃
Or 360 DEG C, preferably 325-345 DEG C.
Preferably, the isothermal reaction time be 2-7h, such as can be 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h,
5.5h, 6h, 6.5h or 7h, preferably 4-5h.
It is a discovery of the invention that in the isothermal reaction temperature range, reactant reaction is more abundant, and product is more stable, reduces
Side reaction probability of happening.
Preferably, the hydrogen chloride gas is passed through after isothermal reaction starts 0.5-2h, is terminated until the reaction is complete.
Preferably, the hydrogen chloride is passed through the time and is after isothermal reaction starts 0.5-2h, for example, can be 0.5h, 0.6h,
0.7h, 0.8h, 0.9h, 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h or 2h.
Preferably, the ventilatory capacity of hydrogen chloride gas be 0.2-1.2L/min, such as can be 0.2L/min, 0.3L/min,
0.4L/min, 0.5L/min, 0.6L/min, 0.7L/min, 0.8L/min, 0.9L/min, 1.0L/min, 1.1L/min or
1.2L/min, preferably 0.5-0.8L/min.
It is a discovery of the invention that be passed through from reaction unit bottom after isothermal reaction 0.5-2h can be with chlorine for the hydrogen chloride gas
Change ammonium and form synergistic effect, under the atmosphere for ensureing isolation air, while can be reacted with samarium oxide and generate samarium trichloride, reduces secondary
The generation of product, and it is passed through hydrogen chloride gas from reaction unit bottom, form vertical friendship with the tiling layer of ammonium chloride and samarium oxide
Fork, keeps the chlorination of samarium oxide more abundant, improves samarium trichloride yield, hydrogen chloride gas recoverable.
Preferably, the mode of the drying is decompression drying.
Preferably, the pressure of the decompression drying be 2.7-6.6kPa, such as can be 2.7kPa, 2.8kPa, 3.0kPa,
3.2kPa、3.5kPa、3.8kPa、4.0kPa、4.2kPa、4.5kPa、4.7kPa、4.9kPa、5.0kPa、5.3kPa、5.5kPa、
5.8kPa, 6.0kPa, 6.1kPa, 6.2kPa, 6.3kPa, 6.4kPa, 6.5kPa or 6.6kPa.
Preferably, the temperature of the decompression drying is 60-110 DEG C, for example, can be 60 DEG C, 62 DEG C, 65 DEG C, 68 DEG C, 70
℃、73℃、75℃、78℃、80℃、82℃、84℃、85℃、86℃、88℃、90℃、92℃、95℃、100℃、101℃、
102 DEG C, 103 DEG C, 104 DEG C, 105 DEG C, 106 DEG C, 107 DEG C, 108 DEG C, 109 DEG C or 110 DEG C, preferably 85 DEG C.
Preferably, the time of the drying be 0.5-3h, such as can be 0.5h, 0.6h, 0.7h, 0.8h, 1.0h,
1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h, 2.0h, 2.2h, 2.5h, 2.8h or 3h.
It is a discovery of the invention that the decompression drying can effectively remove the crystallization water all in samarium trichloride, and in the drying
Under pressure, temperature and drying time range, anhydrous samarium trichloride degree of purity is high, effectively reduces the generation of side reaction.
Preferably, the decompression drying carries out under an inert atmosphere.
Preferably, the inert atmosphere include in argon gas, helium or nitrogen any one or at least two mixture,
The mixture for example can be the mixture of argon gas and helium, the argon gas and mixture of nitrogen or argon gas, helium and nitrogen
Mixture, preferably nitrogen.
It is a discovery of the invention that drying process is easy to happen redox side reaction, decompression baking is carried out under the inert atmosphere
The dry generation that can effectively prevent redox side reaction, keeps drying more abundant, the anhydrous samarium trichloride impurity content of gained is minimum.
Preferably, described method includes following steps：
(1) it pre-processes：Samarium oxide be crushed into 100-160 mesh sieve, ammonium chloride be crushed into 100-150 mesh sieve；
(2) ammonium chloride is laid in reaction unit bottom, tiling thickness is 5-15cm, and samarium oxide is laid in chlorination
On ammonium solid, the mass ratio of samarium oxide and ammonium chloride is 1:(1-3)；
(3) gradient increased temperature, heating rate are 10-20 DEG C/min, and temperature stops heating when reaching 305-360 DEG C, and constant temperature is anti-
It answers, the isothermal reaction time is 2-7h；
(4) isothermal reaction is passed through dry hydrogen chloride gas, ventilatory capacity 0.2-1.2L/min after starting 1-3h；
(5) reaction product that step (4) obtains is subjected to decompression drying 0.5-3h under an inert atmosphere, operating pressure is
2.7-6.6kPa, drying temperature are 60-110 DEG C, obtain anhydrous samarium trichloride.
Second aspect, the present invention provide a kind of anhydrous samarium trichloride that method as described in relation to the first aspect is prepared.
The third aspect, the present invention provide a kind of anhydrous samarium trichloride as described in second aspect for fluxing agent or preparing samarium
Purposes in organo-metallic compound.
Compared with prior art, the present invention has the advantages that：
(1) ammonium chloride and hydrogen chloride gas, and combination matching reactant dosage is used in combination in the present invention, makes ammonium chloride and chlorine
Change hydrogen synergistic effect, adjust each reactant position relationship, keep reaction more abundant, reaction product yield is high, and decompression drying drying is prevented
The only generation of redox side reaction improves product purity, and safe production process is effective, and product purity may be up to 99.6%；
(2) opportunity that the present invention is passed through by adjusting hydrogen chloride gas, reaction temperature and time, keep reaction more abundant,
Side reaction is prevented, the generation of samarium oxychloride is reduced, obtains purer anhydrous samarium trichloride, while present invention process is simple,
The temperature of production is low, easy to operate；
(3) present invention reduces the loss to anhydrous samarium trichloride, yield may be up to by controlling the temperature and time dried
99.3%, water content is down to 0.2%.
Specific implementation mode
Further to illustrate the present invention technological means and its effect taken, below by way of specific implementation mode come into
One step illustrates technical scheme of the present invention, but the present invention is not limited in scope of embodiments.
Embodiment 1
(1) it pre-processes：Samarium oxide be crushed into 130 mesh sieve, ammonium chloride be crushed into 140 mesh sieve；
(2) ammonium chloride is laid in reaction unit bottom, tiling thickness is 8cm, and samarium oxide is laid in ammonium chloride
On solid, the mass ratio of samarium oxide and ammonium chloride is 1:2；
(3) gradient increased temperature, heating rate are 16 DEG C/min, and temperature stops heating, isothermal reaction, constant temperature when reaching 330 DEG C
Reaction time is 4h；
(4) isothermal reaction is passed through dry hydrogen chloride gas, ventilatory capacity 0.6L/min after starting 1h；
(5) reaction product that step (4) obtains is subjected to decompression drying 2h under an inert atmosphere, operating pressure is
3.1kPa, drying temperature are 85 DEG C, obtain anhydrous samarium trichloride.
Embodiment 2
(1) it pre-processes：Samarium oxide be crushed into 140 mesh sieve, ammonium chloride be crushed into 130 mesh sieve；
(2) ammonium chloride is laid in reaction unit bottom, tiling thickness is 12cm, and samarium oxide is laid in ammonium chloride
On solid, the mass ratio of samarium oxide and ammonium chloride is 1:1.5；
(3) gradient increased temperature, heating rate are 12 DEG C/min, and temperature stops heating, isothermal reaction, constant temperature when reaching 360 DEG C
Reaction time is 3h；
(4) isothermal reaction is passed through dry hydrogen chloride gas, ventilatory capacity 0.5L/min after starting 1.5h；
(5) reaction product that step (4) obtains is subjected to decompression drying 1h under an inert atmosphere, operating pressure is
4.2kPa, drying temperature are 103 DEG C, obtain anhydrous samarium trichloride.
Embodiment 3
(1) it pre-processes：Samarium oxide be crushed into 120 mesh sieve, ammonium chloride be crushed into 120 mesh sieve；
(2) ammonium chloride is laid in reaction unit bottom, tiling thickness is 10cm, and samarium oxide is laid in ammonium chloride
On solid, the mass ratio of samarium oxide and ammonium chloride is 1:2.5；
(3) gradient increased temperature, heating rate are 20 DEG C/min, and temperature stops heating, isothermal reaction, constant temperature when reaching 325 DEG C
Reaction time is 5h；
(4) isothermal reaction is passed through dry hydrogen chloride gas, ventilatory capacity 0.8L/min after starting 1h；
(5) reaction product that step (4) obtains is subjected to decompression drying 2.5h under an inert atmosphere, operating pressure is
5.3kPa, drying temperature are 75 DEG C, obtain anhydrous samarium trichloride.
Embodiment 4
(1) it pre-processes：Samarium oxide crushing is sieved with 100 mesh sieve, ammonium chloride crushing is sieved with 100 mesh sieve；
(2) ammonium chloride is laid in reaction unit bottom, tiling thickness is 5cm, and samarium oxide is laid in ammonium chloride
On solid, the mass ratio of samarium oxide and ammonium chloride is 1:1；
(3) gradient increased temperature, heating rate are 10 DEG C/min, and temperature stops heating, isothermal reaction, constant temperature when reaching 305 DEG C
Reaction time is 2h；
(4) isothermal reaction is passed through dry hydrogen chloride gas, ventilatory capacity 1.2L/min after starting 0.5h；
(5) reaction product that step (4) obtains is subjected to decompression drying 0.5h under an inert atmosphere, operating pressure is
6.6kPa, drying temperature are 110 DEG C, obtain anhydrous samarium trichloride.
Embodiment 5
(1) it pre-processes：Samarium oxide be crushed into 160 mesh sieve, ammonium chloride be crushed into 150 mesh sieve；
(2) ammonium chloride is laid in reaction unit bottom, tiling thickness is 15cm, and samarium oxide is laid in ammonium chloride
On solid, the mass ratio of samarium oxide and ammonium chloride is 1:3；
(3) gradient increased temperature, heating rate are 15 DEG C/min, and temperature stops heating, isothermal reaction, constant temperature when reaching 345 DEG C
Reaction time is 7h；
(4) isothermal reaction is passed through dry hydrogen chloride gas, ventilatory capacity 0.2L/min after starting 2h；
(5) reaction product that step (4) obtains is subjected to decompression drying 3h under an inert atmosphere, operating pressure is
2.7kPa, drying temperature are 60 DEG C, obtain anhydrous samarium trichloride.
Embodiment 6
Compared with Example 1, the pretreatment without samarium oxide and ammonium chloride, other conditions are the same as embodiment 1.
Embodiment 7
Compared with Example 1, the mesh number that pulverizes and sieves of samarium oxide is 80 mesh, and other conditions are the same as embodiment 1.
Embodiment 8
Compared with Example 1, the mesh number that pulverizes and sieves of samarium oxide is 200 mesh, and other conditions are the same as embodiment 1.
Embodiment 9
Compared with Example 1, the mesh number that pulverizes and sieves of ammonium chloride is 80 mesh, and other conditions are the same as embodiment 1.
Embodiment 10
Compared with Example 1, the mesh number that pulverizes and sieves of ammonium chloride is 180 mesh, and other conditions are the same as embodiment 1.
Embodiment 11
Compared with embodiment 1, samarium oxide is laid in reaction unit bottom, then ammonium chloride is laid on samarium oxide,
Other conditions are the same as embodiment 1.
Embodiment 12
Compared with embodiment 1, the mass ratio of samarium oxide and ammonium chloride is 1:0.2, other conditions are the same as embodiment 1.
Embodiment 13
Compared with embodiment 1, the mass ratio of samarium oxide and ammonium chloride is 1:4, other conditions are the same as embodiment 1.
Embodiment 14
Compared with embodiment 1, the tiling layer thickness of ammonium chloride is 2cm, and other conditions are the same as embodiment 1.
Embodiment 15
Compared with embodiment 1, the tiling layer thickness of ammonium chloride is 20cm, and other conditions are the same as embodiment 1.
Embodiment 16
Compared with embodiment 1, gradient increased temperature mode is not used, reaction unit is directly warming up to 330 DEG C, other conditions are same
Embodiment 1.
Embodiment 17
Compared with embodiment 1, gradient increased temperature is to 280 DEG C and starts isothermal reaction, and other conditions are the same as embodiment 1.
Embodiment 18
Compared with embodiment 1, gradient increased temperature is to 380 DEG C and starts isothermal reaction, and other conditions are the same as embodiment 1.
Embodiment 19
Compared with embodiment 1, gradient increased temperature rate is 5 DEG C/min, other reaction conditions are the same as embodiment 1.
Embodiment 20
Compared with embodiment 1, gradient increased temperature rate is 30 DEG C/min, other reaction conditions are the same as embodiment 1.
Embodiment 21
Compared with embodiment 1, it is passed through dry hydrogen chloride gas before reaching constant temperature, other conditions are the same as embodiment 1.
Embodiment 22
Compared with embodiment 1, isothermal reaction is passed through dry hydrogen chloride gas after starting 4h, and other conditions are same
Embodiment 1.
Embodiment 23
Compared with embodiment 1, the ventilatory capacity of hydrogen chloride is 1.5L/min, and other conditions are the same as embodiment 1.
Embodiment 24
Compared with embodiment 1, dries and carried out under normal pressure again, other conditions are the same as embodiment 1.
Comparative example 1
Compared with Example 1, ammonium chloride is not added, other conditions are the same as embodiment 1.
Comparative example 2
Compared with Example 1, hydrogen chloride gas is not added, other conditions are the same as embodiment 1.
The calculating that purity, water content and yield are carried out to the product that embodiment 1-24 and comparative example 1-2 are obtained, the results are shown in Table
1。
Table 1
Comparing embodiment 1 with embodiment 6-10 it is found that pretreatment mode of the present invention can effectively facilitate react fully into
Row improves yield；Comparing embodiment 1 and embodiment 11-15 it is found that reactant of the present invention modes of emplacement and mass-energy density
Yield is effectively improved, the generation of by-product is reduced, improves product purity；Comparing embodiment 1 is with embodiment 16-20 it is found that reacting
The influence of mode of heating, heating rate and isothermal reaction time to yield, water content and purity, in condition model of the present invention
Uniformity of temperature profile can be effectively facilitated under enclosing, and reduce side reaction；Comparing embodiment 1 and embodiment 21-23 is it is found that hydrogen chloride gas
Be passed through the influence of opportunity and ventilatory capacity to efficiency of pcr product, water content and purity；Comparing embodiment 1 is with embodiment 24 it is found that subtracting
Pressure drying can effectively improve purity in the pressure, temperature and time, reduce water content；Comparing embodiment 1 and comparative example 1-2
It is found that ammonium chloride and hydrogen chloride gas synergy, indispensable.
To sum up, the present invention utilizes ammonium chloride and hydrogen chloride gas by combination, determines optimum response mode and condition, obtains
Water content is low, and purity is high, the high anhydrous samarium trichloride of yield, has broad prospect of application.
Applicant states that the present invention illustrates the method detailed of the present invention, but the present invention not office by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, the selection etc. of concrete mode, all fall within protection scope of the present invention and the open scope.
Claims (10)
1. a kind of preparation method of anhydrous samarium trichloride, which is characterized in that using samarium oxide as raw material, carried out using chloride solid anti-
It answers, then is passed through dry hydrogen chloride gas, be heated to that the reaction was complete, product is dried, anhydrous samarium trichloride is obtained.
2. according to the method described in claim 1, it is characterized in that, the method further includes pretreated step；
Preferably, the pretreatment specifically includes：The samarium oxide and ammonium chloride are pulverized and sieved；
Preferably, the mesh number of the samarium oxide sieving is 100-160 mesh, preferably 120-140 mesh；
Preferably, the mesh number of the ammonium chloride sieving is 100-150 mesh.
3. method according to claim 1 or 2, which is characterized in that the chloride solid is laid in reaction unit bottom,
Samarium oxide is laid on chloride solid；
Preferably, the mass ratio of the samarium oxide and ammonium chloride is 1:(1-3), preferably 1:2；
Preferably, the ammonium chloride tiling thickness is 5-15cm, preferably 8cm.
4. according to claim 1-3 any one of them methods, which is characterized in that the heating is by the way of gradient increased temperature；
Preferably, the rate of the heating is 10-20 DEG C/min.
Preferably, described to carry out isothermal reaction, preferably 325-345 DEG C when being warming up to 305-360 DEG C；
Preferably, the isothermal reaction time is 2-7h, preferably 4-5h.
5. according to claim 1-4 any one of them methods, which is characterized in that the hydrogen chloride gas starts in isothermal reaction
It is passed through after 0.5-2h, terminates until the reaction is complete；
Preferably, the ventilatory capacity of hydrogen chloride gas is 0.2-1.2L/min, preferably 0.5-0.8L/min.
6. according to claim 1-5 any one of them methods, which is characterized in that the mode of the drying is decompression drying；
Preferably, the pressure of the decompression drying is 2.7-6.6kPa；
Preferably, the temperature of the decompression drying is 60-110 DEG C, preferably 85 DEG C；
Preferably, the time of the decompression drying is 0.5-3h.
7. according to claim 1-6 any one of them methods, which is characterized in that the decompression drying under an inert atmosphere into
Row；
Preferably, the inert atmosphere include in argon gas, helium or nitrogen any one or at least two mixture, preferably
For nitrogen.
8. according to claim 1-7 any one of them methods, which is characterized in that include the following steps：
(1) it pre-processes：Samarium oxide be crushed into 100-160 mesh sieve, ammonium chloride be crushed into 100-150 mesh sieve；
(2) ammonium chloride is laid in reaction unit bottom, tiling thickness is 5-15cm, and samarium oxide is laid in ammonium chloride and is consolidated
On body, the mass ratio of samarium oxide and ammonium chloride is 1:(1-3)；
(3) gradient increased temperature, heating rate are 10-20 DEG C/min, and temperature stops heating when reaching 305-360 DEG C, isothermal reaction is permanent
The warm reaction time is 2-7h；
(4) isothermal reaction is passed through dry hydrogen chloride gas, ventilatory capacity 0.2-1.2L/min after starting 1-3h；
(5) reaction product that step (4) obtains is subjected to decompression drying 0.5-3h, operating pressure 2.7- under an inert atmosphere
6.6kPa, drying temperature are 60-110 DEG C, obtain anhydrous samarium trichloride.
9. a kind of anhydrous samarium trichloride being prepared such as claim 1-8 any one of them methods.
10. a kind of anhydrous samarium trichloride as claimed in claim 9 is for fluxing agent or prepares in the organo-metallic compound of samarium
Purposes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810394683.1A CN108455650A (en) | 2018-04-27 | 2018-04-27 | A kind of preparation method of anhydrous samarium trichloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810394683.1A CN108455650A (en) | 2018-04-27 | 2018-04-27 | A kind of preparation method of anhydrous samarium trichloride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108455650A true CN108455650A (en) | 2018-08-28 |
Family
ID=63236224
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810394683.1A Pending CN108455650A (en) | 2018-04-27 | 2018-04-27 | A kind of preparation method of anhydrous samarium trichloride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108455650A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110065963A (en) * | 2019-04-26 | 2019-07-30 | 兰州大学 | A kind of preparation method of anhydrous rare-earth chlorination |
| CN111186853A (en) * | 2018-10-26 | 2020-05-22 | 北京梦晖科技有限公司 | Preparation method of rare earth halide |
| CN112010339A (en) * | 2020-09-04 | 2020-12-01 | 内蒙古蒙稀新材料有限责任公司 | Preparation method of high-purity anhydrous rare earth chloride |
| CN113772715A (en) * | 2021-10-18 | 2021-12-10 | 天津包钢稀土研究院有限责任公司 | Anhydrous samarium chloride and preparation method thereof |
| CN113772714A (en) * | 2021-10-18 | 2021-12-10 | 天津包钢稀土研究院有限责任公司 | Anhydrous samarium chloride and preparation method thereof |
| CN116443914A (en) * | 2023-03-26 | 2023-07-18 | 长江大学 | Preparation method and application of halide solid electrolyte |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1785814A (en) * | 2005-12-26 | 2006-06-14 | 包头市世博稀土冶金有限责任公司 | Preparation method of anhydrous cerium chloride |
| CN104326502A (en) * | 2014-11-06 | 2015-02-04 | 赣州有色冶金研究所 | Method and device for preparing anhydrous rare earth chloride through gas phase method |
| CN107827140A (en) * | 2017-09-12 | 2018-03-23 | 中国科学院青海盐湖研究所 | The preparation method of anhydrous rare-earth chlorination |
-
2018
- 2018-04-27 CN CN201810394683.1A patent/CN108455650A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1785814A (en) * | 2005-12-26 | 2006-06-14 | 包头市世博稀土冶金有限责任公司 | Preparation method of anhydrous cerium chloride |
| CN100357183C (en) * | 2005-12-26 | 2007-12-26 | 包头市世博稀土冶金有限责任公司 | Preparation method of anhydrous cerium chloride |
| CN104326502A (en) * | 2014-11-06 | 2015-02-04 | 赣州有色冶金研究所 | Method and device for preparing anhydrous rare earth chloride through gas phase method |
| CN107827140A (en) * | 2017-09-12 | 2018-03-23 | 中国科学院青海盐湖研究所 | The preparation method of anhydrous rare-earth chlorination |
Non-Patent Citations (1)
| Title |
|---|
| 褚意新: "NH4Cl（s）焙烧氯化Sm2O3（s）及其动力学研究", 《河南科学》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111186853A (en) * | 2018-10-26 | 2020-05-22 | 北京梦晖科技有限公司 | Preparation method of rare earth halide |
| CN110065963A (en) * | 2019-04-26 | 2019-07-30 | 兰州大学 | A kind of preparation method of anhydrous rare-earth chlorination |
| CN112010339A (en) * | 2020-09-04 | 2020-12-01 | 内蒙古蒙稀新材料有限责任公司 | Preparation method of high-purity anhydrous rare earth chloride |
| CN112010339B (en) * | 2020-09-04 | 2021-06-18 | 内蒙古蒙稀新材料有限责任公司 | Preparation method of high-purity anhydrous rare earth chloride |
| CN113772715A (en) * | 2021-10-18 | 2021-12-10 | 天津包钢稀土研究院有限责任公司 | Anhydrous samarium chloride and preparation method thereof |
| CN113772714A (en) * | 2021-10-18 | 2021-12-10 | 天津包钢稀土研究院有限责任公司 | Anhydrous samarium chloride and preparation method thereof |
| CN113772715B (en) * | 2021-10-18 | 2023-06-23 | 天津包钢稀土研究院有限责任公司 | Anhydrous samarium chloride and preparation method thereof |
| CN116443914A (en) * | 2023-03-26 | 2023-07-18 | 长江大学 | Preparation method and application of halide solid electrolyte |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108455650A (en) | A kind of preparation method of anhydrous samarium trichloride | |
| CN106684485B (en) | Method for recycling waste lithium iron phosphate anode material by acid leaching method | |
| US20180219253A1 (en) | Method for producing garnet type oxide solid electrolyte | |
| CN108298573A (en) | A kind of preparation method of anhydrous yttrium chloride | |
| CN104528703A (en) | Preparation method of nitrogen/phosphorus-codoped graphene | |
| CN104627972B (en) | A kind of preparation method of phosphatization powder for lithium | |
| CN104555959A (en) | Method for preparing lithium hexafluorophosphate quickly | |
| CN110171832A (en) | A method of porous silicon is prepared based on metal hydride reduction | |
| JPH1171113A (en) | Manganese oxide thin film and its production | |
| CN103011114A (en) | Method of producing monopotassium phosphate | |
| CN100513305C (en) | Polycrystalline LiFePO4 powder solid phase-microwave synthesis method | |
| CN102390856A (en) | Method for preparing high-stability gamma-phase nanometer lanthanum sulfide powder in low temperature | |
| CN204079519U (en) | Vapor phase process prepares the system of anhydrous chlorides of rase earth elements | |
| CN110342542A (en) | A kind of synthetic method of nitrolim | |
| KR101722963B1 (en) | Method For Producing Magnesium Hydroxide Powder By Semidry Process | |
| CN115959644A (en) | Method for preparing high-performance lithium iron phosphate by sectional sintering | |
| CN114890402A (en) | Preparation method of hexafluorophosphate | |
| CN106745287A (en) | A kind of preparation method of high-pure anhydrous manganese chloride | |
| CN108493449B (en) | Controllable preparation method of sodium manganese fluorophosphate cathode material | |
| CN111036259A (en) | Preparation method of fluorine-doped carbon nitride nanosheet | |
| CN106365201A (en) | Highly-pure zinc arsenide preparation device and method | |
| JPH0781903A (en) | Production of inorganic fluoride being in gaseous state at ordinary temperature | |
| CN113024284B (en) | Method for preparing nitrogen-phosphorus-potassium compound fertilizer by fertilizer-grade phosphoric acid eutectic | |
| CN105428667B (en) | A kind of preparation method of cathode material for solid-oxide fuel cell | |
| JP2002234719A (en) | Apparatus for producing silicon material and method therefor |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180828 |
|
| RJ01 | Rejection of invention patent application after publication |