CN114920278B - Anhydrous scandium trichloride, and preparation method and application thereof - Google Patents
Anhydrous scandium trichloride, and preparation method and application thereof Download PDFInfo
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- CN114920278B CN114920278B CN202210596996.1A CN202210596996A CN114920278B CN 114920278 B CN114920278 B CN 114920278B CN 202210596996 A CN202210596996 A CN 202210596996A CN 114920278 B CN114920278 B CN 114920278B
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- DVMZCYSFPFUKKE-UHFFFAOYSA-K scandium chloride Chemical compound Cl[Sc](Cl)Cl DVMZCYSFPFUKKE-UHFFFAOYSA-K 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910001868 water Inorganic materials 0.000 claims abstract description 49
- FKZFOHABAHJDIK-UHFFFAOYSA-K trichloroscandium;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Sc+3] FKZFOHABAHJDIK-UHFFFAOYSA-K 0.000 claims abstract description 46
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000001354 calcination Methods 0.000 claims abstract description 32
- 239000003960 organic solvent Substances 0.000 claims abstract description 31
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001704 evaporation Methods 0.000 claims abstract description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012043 crude product Substances 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims abstract description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000008020 evaporation Effects 0.000 claims abstract description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 64
- 239000000243 solution Substances 0.000 claims description 30
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 22
- 235000011837 pasties Nutrition 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000000047 product Substances 0.000 abstract description 19
- 229910052706 scandium Inorganic materials 0.000 abstract description 17
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052751 metal Inorganic materials 0.000 abstract description 13
- 239000013078 crystal Substances 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 6
- 239000013110 organic ligand Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000000460 chlorine Substances 0.000 description 12
- 235000002639 sodium chloride Nutrition 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- CJTKCSUNRNSKAD-UHFFFAOYSA-N [Sc].O(Cl)Cl Chemical compound [Sc].O(Cl)Cl CJTKCSUNRNSKAD-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000004687 hexahydrates Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- -1 and in recent years Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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
- 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
- C01F17/10—Preparation or treatment, e.g. separation or purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The application relates to the technical field of chemical synthesis, in particular to anhydrous scandium trichloride, and a preparation method and application thereof. The preparation method comprises the following steps: scandium trichloride hexahydrate, sulfoxide chloride and an organic solvent are mixed and reacted for 10 to 24 hours at the temperature of 15 to 60 ℃, and then the residual organic solvent and sulfoxide chloride are removed by evaporation to prepare a crude product; calcining the crude product in a non-reactive gas atmosphere to prepare anhydrous scandium trichloride; wherein the organic solvent comprises one or more of tetrahydrofuran, acetonitrile, pyridine, methanol and ethylene glycol dimethyl ether. By introducing an organic solvent, a stable metal organic complex is formed with the scandium metal center, so that crystal water in scandium trichloride hexahydrate is replaced, and the introduced organic ligand is removed in a calcining manner, so that anhydrous scandium trichloride with high purity can be prepared. Meanwhile, the sulfoxide chloride which can react with the crystal water and generate volatile gas is introduced, so that the purity of the product is further improved.
Description
Technical Field
The application relates to the technical field of chemical synthesis, in particular to anhydrous scandium trichloride, and a preparation method and application thereof.
Background
The transition metal complexes, owing to their excellent catalytic activity, are of major importance in modern organic synthesis. Thanks to the use of transition metal complexes, a number of completely new catalytic reaction systems are rapidly developed and applied. The precursors of transition metal complexes are often their corresponding anhydrous chlorides, and therefore, in order to ensure the catalytic properties of the transition metal complexes, it is also important to control the quality of the anhydrous chlorides.
The rare earth scandium is also a transition metal, and in recent years, scandium catalysts have been considered as transition metal catalysts having development potential because scandium has a relatively large content in the crust, because scandium has developed to exhibit unique activities, regions and stereoselectivities in the fields of hydrocarbon bond activation and the like. However, scandium is too dispersed although the content is large, which results in a relatively complex extraction and separation process of scandium. Meanwhile, scandium is used as a relatively active metal, is easily combined with acid, oxygen, carbon dioxide, water and the like, and loses the luster like lead. Therefore, the anhydrous scandium trichloride with high purity is difficult to prepare in the traditional technology, particularly the scandium trichloride is easy to hydrolyze in the water removal step, and the preparation technology is complex, the condition is harsh, the danger coefficient is high, and the industrial production is not facilitated.
Disclosure of Invention
Based on the above, it is necessary to provide an anhydrous scandium trichloride, and a preparation method and application thereof, wherein the preparation method can avoid hydrolysis of scandium trichloride caused by a water removal step in the traditional process, and the prepared anhydrous scandium trichloride has higher purity and better quality.
In one aspect of the present application, there is provided a method for preparing anhydrous scandium trichloride, comprising the steps of:
scandium trichloride hexahydrate, sulfoxide chloride and an organic solvent are mixed and reacted for 10 to 24 hours at the temperature of 15 to 60 ℃, and then the residual organic solvent and sulfoxide chloride are removed by evaporation to prepare a crude product; calcining the crude product in a non-reactive gas atmosphere to prepare anhydrous scandium trichloride;
wherein the organic solvent comprises one or more of tetrahydrofuran, acetonitrile, pyridine, methanol and ethylene glycol dimethyl ether.
In some embodiments, the amount of the organic solvent is 2mL or more per 1g of scandium trichloride hexahydrate.
In some embodiments, the amount of sulfoxide chloride per 1g of scandium trichloride hexahydrate is 2mL or greater.
In some embodiments, the calcination is at a temperature of 400 ℃ to 600 ℃ and the calcination is for a time of 2 hours to 5 hours.
In some embodiments, the temperature of the evaporation is from 40 ℃ to 100 ℃.
In some embodiments, the scandium trichloride hexahydrate is in the form of a pasty scandium trichloride hexahydrate containing free water, and the method for producing the pasty scandium trichloride hexahydrate comprises the steps of:
scandium oxide is dissolved in a hydrochloric acid aqueous solution to prepare a scandium trichloride solution; heating the scandium trichloride solution at the temperature of 100-180 ℃ to obtain the pasty scandium trichloride hexahydrate.
In some embodiments, the mass percentage of free water not combined with scandium trichloride in the pasty scandium trichloride hexahydrate is 3% -8%.
In some embodiments, the hydrochloric acid aqueous solution has a mass percent of hydrochloric acid of 30-38%.
In some embodiments, the amount of the aqueous hydrochloric acid solution corresponding to each 1g of scandium oxide is 5mL to 10mL.
In some embodiments, the dissolving scandium oxide in aqueous hydrochloric acid is performed at a temperature of 80℃to 150 ℃.
In another aspect of the application, there is also provided anhydrous scandium trichloride, which is produced by the production method of any one of the preceding embodiments.
In yet another aspect of the present application, there is also provided the use of the aforementioned anhydrous scandium trichloride in the preparation of a metal scandium complex.
According to the application, organic solvents such as tetrahydrofuran and the like are innovatively introduced to form a stable metal organic complex with the scandium metal center, so that crystal water in scandium trichloride hexahydrate is replaced, and the introduced organic ligand is removed in a calcining manner, so that the anhydrous scandium trichloride with high purity can be prepared. Meanwhile, the sulfoxide chloride which can react with the crystal water and generate volatile gas is introduced, so that the coordination between the organic solvent and the metal center can be promoted, the residual moisture can be reduced, and the purity of the product is further improved. Effectively solves the problems that scandium trichloride is easy to hydrolyze due to water removal in the prior art or the introduced additive is difficult to remove, so that the purity of the product is reduced. In addition, the preparation method is simple to operate and easy for industrial production, and the preparation process which is difficult and complex in conditions such as chlorine calcination and the like, dangerous and not environment-friendly in the traditional technology is avoided.
Detailed Description
In order that the application may be readily understood, a more particular description of the application will be rendered by reference to specific embodiments that are illustrated in the appended drawings. This application may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the application, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise. In the description of the present application, the meaning of "several" means at least one, such as one, two, etc., unless specifically defined otherwise.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
In the application, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise an open technical scheme comprising the listed characteristics.
In the present application, the numerical ranges are referred to as continuous, and include the minimum and maximum values of the ranges, and each value between the minimum and maximum values, unless otherwise specified. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range description features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
The percentage content referred to in the present application refers to mass percentage for both solid-liquid mixing and solid-solid mixing and volume percentage for liquid-liquid mixing unless otherwise specified.
The percentage concentrations referred to in the present application refer to the final concentrations unless otherwise specified. The final concentration refers to the ratio of the additive component in the system after the component is added.
The temperature parameter in the present application is not particularly limited, and may be a constant temperature treatment or a treatment within a predetermined temperature range. The constant temperature process allows the temperature to fluctuate within the accuracy of the instrument control.
In the present application, "non-reactive gas atmosphere" means any gas atmosphere which does not react with the crude product to be calcined, and may be, for example, nitrogen or argon.
In the conventional technology, anhydrous scandium trichloride is mainly prepared by the following methods: (1) Dissolving scandium oxide in hydrochloric acid aqueous solution in a reflux way, adding ammonium hydroxide solution, heating, boiling for water removal, drying the obtained wet solid in vacuum at room temperature overnight, and further removing water and purifying through fractional calcination, wherein the yield of the method can only reach about 64 percent due to the problems of decomposition and the like during water removal; (2) Calcining anhydrous scandium oxide and carbon black at 900 ℃ in a chlorine atmosphere, and treating under an argon protective atmosphere after the reaction is finished to obtain anhydrous scandium trichloride crystals with larger granularity; (3) Slowly heating and melting aluminum chloride and scandium oxide at 220-280 ℃, then heating to more than 500 ℃ for calcining to remove redundant aluminum trichloride; (4) Mixing a mixed solution of sodium chloride, potassium chloride and ammonium chloride with a scandium oxide solution dissolved by concentrated hydrochloric acid, heating and evaporating twice to remove redundant hydrogen chloride, free water and crystal water to obtain anhydrous scandium chloride molten salt, calcining at about 500 ℃ under vacuum condition, and removing ammonium chloride to obtain anhydrous scandium trichloride, wherein the addition of inorganic salts such as sodium chloride, potassium chloride and ammonium chloride is used for stabilizing scandium chloride, avoiding the hydrolysis of scandium chloride in the water removal process as much as possible, and improving the water absorption of scandium chloride.
However, these methods are either prone to hydrolysis, low in yield and purity, require harsh conditions such as calcination in a chlorine atmosphere at 900 ℃, or require the introduction of difficult to remove aluminum, sodium, potassium, and other miscellaneous elements, and in short, it is difficult to obtain high purity anhydrous scandium trichloride in a relatively simple and easy-to-industrialize preparation process.
Based on the above background, the present inventors have made extensive studies to provide a method for producing anhydrous scandium trichloride, which comprises the steps of:
scandium trichloride hexahydrate, sulfoxide chloride and an organic solvent are mixed and reacted for 10 to 24 hours at the temperature of 15 to 60 ℃, and then the residual organic solvent and sulfoxide chloride are removed by evaporation to prepare a crude product; calcining the crude product in a non-reactive gas atmosphere to prepare anhydrous scandium trichloride;
wherein the organic solvent comprises one or more of tetrahydrofuran, acetonitrile, pyridine, methanol and ethylene glycol dimethyl ether.
By innovatively introducing organic solvents such as tetrahydrofuran and the like, a stable metal-organic complex is formed with the scandium metal center, so that crystal water in scandium trichloride hexahydrate is replaced, and the introduced organic ligand is removed in a calcining manner, so that the anhydrous scandium trichloride with high purity can be prepared. Meanwhile, the sulfoxide chloride which can react with the crystal water and generate volatile gas is introduced, so that the coordination between the organic solvent and the metal center can be promoted, the residual moisture can be reduced, and the purity of the product is further improved. Effectively solves the problems that scandium trichloride is easy to hydrolyze due to water removal in the prior art or the introduced additive is difficult to remove, so that the purity of the product is reduced. In addition, the preparation method is simple to operate and easy for industrial production, and the preparation process which is difficult and complex in conditions such as chlorine calcination and the like, dangerous and not environment-friendly in the traditional technology is avoided.
Preferably, the organic solvent is selected from one or more of tetrahydrofuran, methanol and acetonitrile.
Further preferably, tetrahydrofuran is selected as the organic solvent, and compared with other organic solvents, tetrahydrofuran can better replace crystal water in scandium trichloride hexahydrate, and is easier to remove during calcination, so that the yield of the product is higher.
In some embodiments, the temperature of the reaction may also be, for example, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃,50 ℃ or 55 ℃, preferably 20 ℃ to 30 ℃. The proper reaction temperature can enable the organic solvent to smoothly replace crystal water in scandium trichloride hexahydrate, and the volatilization or decomposition of the reaction raw materials can not be caused.
In some embodiments, the time of the reaction may also be, for example, 12h, 14h, 16h, 18h, 20h, or 22h. Preferably, the reaction time is from 10h to 14h. The proper reaction time can lead the organic solvent to be completely coordinated with the center of the scandium metal, and avoid side reactions.
In some embodiments, the amount of organic solvent is 2mL or more per 1g scandium trichloride hexahydrate. The amount of the organic solvent used per 1g of scandium trichloride hexahydrate may be, for example, 4mL, 6mL, 8mL, 10mL, 12mL, 14mL or 16mL. Preferably, the amount of the organic solvent is 2 mL-10 mL for every 1g of scandium trichloride hexahydrate. The proper amount of organic solvent can enable the crystalline water in scandium trichloride hexahydrate to be replaced completely and be removed more easily later.
In some embodiments, the amount of sulfoxide chloride corresponding to scandium trichloride hexahydrate is 2mL or greater per 1g of scandium trichloride. The amount of thionyl chloride corresponding to scandium trichloride hexahydrate per 1g may be, for example, 4mL, 6mL, 8mL, 10mL, 12mL, 14mL or 16mL. Preferably, the dosage of sulfoxide chloride corresponding to each 1g of scandium trichloride hexahydrate is 2-10 mL. The proper dosage of the thionyl chloride can help to remove the crystallization water in scandium trichloride hexahydrate, so that the metal center is more easily coordinated with the organic solvent, the purity of the product is further improved, and the subsequent removal is easier.
In the "… … corresponding to scandium trichloride per 1g of hexahydrate" mentioned in the foregoing embodiment, "scandium trichloride per 1g of hexahydrate" means that the mass of pure scandium trichloride hexahydrate is 1g, excluding the mass of other components. For example, when the form of "scandium trichloride hexahydrate is pasty scandium trichloride containing free water", the total mass of scandium trichloride hexahydrate containing free water should be calculated from the mass of scandium trichloride hexahydrate of 1g and the mass percentage of free water in scandium trichloride hexahydrate, and the paste scandium trichloride hexahydrate containing free water is taken out, but the paste scandium trichloride hexahydrate cannot be taken out directly at a mass of 1 g.
In some embodiments, the calcination temperature is 400 ℃ to 600 ℃ and the calcination time is 2 hours to 5 hours. Preferably, the calcination temperature is 500 ℃ to 550 ℃. The temperature of the calcination may be 420 ℃, 440 ℃, 460 ℃, 480 ℃,500 ℃, 520 ℃, 540 ℃, 560 ℃ or 580 ℃, for example. The calcination time may also be, for example, 3 hours or 4 hours. The proper calcination temperature and calcination time can thoroughly remove tetrahydrofuran combined with scandium metal center, avoid residue of miscellaneous elements and can not lead to melting of the product.
In some embodiments, the temperature of evaporation is from 40 ℃ to 100 ℃. Preferably, the temperature of evaporation is 60℃to 80 ℃. The excessive organic solvent and sulfoxide chloride can be thoroughly removed at a proper evaporation temperature, and the bumping is not caused.
In some embodiments, the scandium trichloride hexahydrate is in the form of a pasty scandium trichloride hexahydrate containing free water, the method for producing the pasty scandium trichloride hexahydrate comprising the steps of:
scandium oxide is dissolved in a hydrochloric acid aqueous solution to prepare a scandium trichloride solution; heating the scandium trichloride solution at the temperature of 100-180 ℃ to obtain pasty scandium trichloride hexahydrate. The scandium trichloride solution is heated to be pasty, certain free water is reserved, and the phenomenon that scandium trichloride is hydrolyzed to generate scandium oxychloride due to the fact that all water is evaporated to dryness can be avoided, so that the purity of the product is reduced.
Preferably, the scandium trichloride solution is heated to a temperature of 120℃to 150 ℃. Proper heating temperature can make the dewatering time faster, and can not cause the bumping, is difficult to control the dewatering volume. The heating temperature may also be 140℃or 160℃for example.
In some embodiments, the mass percentage of free water in the pasty scandium trichloride that is not bound to scandium trichloride is 3% to 8%. The mass percentage of free water may also be, for example, 4%, 5%, 6% or 7%. The content of free water is controlled within a proper range, so that scandium trichloride is not hydrolyzed, and meanwhile, the crystallization water in scandium trichloride hexahydrate can be thoroughly replaced by an organic solvent in the subsequent step.
In some embodiments, the mass percent of hydrochloric acid in the aqueous hydrochloric acid solution is 30% -38%. The mass percentage of hydrochloric acid in the aqueous hydrochloric acid solution may be, for example, 32%, 34% or 36%. Suitable hydrochloric acid concentrations enable scandium oxide to be dissolved more thoroughly. Preferably, the incorporation of impurities can be further reduced by using an electronic grade aqueous hydrochloric acid solution.
In some embodiments, the amount of aqueous hydrochloric acid solution corresponding to each 1g scandium oxide is 5 mL-10 mL. The amount of the aqueous hydrochloric acid solution to be used per 1g of scandium oxide may be, for example, 6mL or 8mL. Suitable amounts of aqueous hydrochloric acid allow for thorough dissolution of scandium oxide and subsequent easier removal.
In some embodiments, the dissolving of scandium oxide in aqueous hydrochloric acid is performed at a temperature of 80℃to 150 ℃. Preferably, the dissolution of scandium oxide in aqueous hydrochloric acid is carried out at a temperature of 100℃to 120 ℃. The operating temperature at which scandium oxide is dissolved in aqueous hydrochloric acid can also be, for example, 90 ℃, 110 ℃ or 130 ℃. The dissolution temperature is related to the dissolution degree and dissolution rate of scandium oxide, and incorrect temperature setting can lead to incomplete dissolution of scandium oxide, introduction of impurities and reduction of yield.
In another aspect of the application, there is also provided anhydrous scandium trichloride, which is produced by the production method of any one of the preceding embodiments. The anhydrous scandium trichloride prepared by the preparation method has higher purity and fewer impurity elements than the anhydrous scandium trichloride prepared by the traditional technology.
In yet another aspect of the present application, there is also provided the use of the aforementioned anhydrous scandium trichloride in the preparation of a metal scandium complex.
The present application will be described in further detail with reference to specific examples and comparative examples. The experimental parameters not specified in the following specific examples are preferentially referred to the guidelines given in the present document, and may also be referred to the experimental manuals in the art or other experimental methods known in the art, or to the experimental conditions recommended by the manufacturer. It is understood that the apparatus and materials used in the following examples are more specific and in other embodiments may not be so limited; the weights of the relevant components mentioned in the embodiments of the present application may refer not only to the specific contents of the components, but also to the proportional relationship between the weights of the components, and thus, it is within the scope of the embodiments of the present application as long as the contents of the relevant components are scaled up or down according to the embodiments of the present application. Specifically, the weight described in the specification of the embodiment of the present application may be mass units known in the chemical field such as μ g, mg, g, kg.
Example 1
(1) 4.8g of scandium oxide is weighed and dissolved in 35mL of concentrated hydrochloric acid (38 wt% hydrochloric acid aqueous solution) under the heating condition of 110 ℃ to obtain clear scandium chloride solution;
(2) Heating and evaporating the clear scandium chloride solution prepared in the step (1) at 135 ℃ to remove most of free water and all HCl in the solution, so as to obtain pasty scandium chloride hexahydrate with the mass percent of the free water being about 5%;
(3) Dissolving the pasty scandium trichloride hexahydrate prepared in the step (2) in 40mL of tetrahydrofuran, then adding 40mL of thionyl chloride, and stirring for 12h at room temperature; then heating and evaporating at 80 ℃ until no liquid residue exists, and obtaining a crude product;
(4) Calcining the crude product prepared in the step (3) in a dry argon atmosphere at 500 ℃ for 3 hours to obtain an anhydrous scandium trichloride product.
Example 2
(1) 4.2g of scandium oxide is weighed and dissolved in 35mL of concentrated hydrochloric acid (38 wt% hydrochloric acid aqueous solution) under the heating condition of 110 ℃ to obtain clear scandium chloride solution;
(2) Heating and evaporating the clear scandium chloride solution prepared in the step (1) at 135 ℃ to remove most of free water and all HCl in the solution, so as to obtain pasty scandium chloride hexahydrate with the mass percent of the free water being about 5%;
(3) Dissolving the pasty scandium trichloride hexahydrate prepared in the step (2) in 35mL of tetrahydrofuran, then adding 35mL of thionyl chloride, and stirring for 12h at room temperature; then heating and evaporating at 80 ℃ until no liquid residue exists, and obtaining a crude product;
(4) Calcining the crude product prepared in the step (3) for 3 hours at 550 ℃ in a dry argon atmosphere to obtain an anhydrous scandium trichloride product.
Example 3
Substantially the same as in example 1, except that the calcination temperature in step (4) was modified to 400 ℃.
Example 4
Substantially the same as in example 1, except that tetrahydrofuran in step (3) was changed to acetonitrile of equal volume.
Example 5
Substantially the same as in example 1, except that tetrahydrofuran in step (3) was changed to methanol of equal volume.
Example 6
Substantially the same as in example 1, except that tetrahydrofuran in step (3) was changed to pyridine in an equal volume.
Comparative example 1
Scandium chloride solution was prepared by dissolving 10g of scandium oxide having a purity of 99.0% with 50mL of 30% hydrochloric acid at a heating temperature of 90 ℃. Configuration NH 4 Cl solution, then scandium chloride solution is reacted with NH 4 Mixing Cl solution, scandium chloride and NH 4 The mass ratio of Cl is 1: and 3, filtering out residues after stirring to obtain scandium chloride mixed molten salt solution. And heating the scandium chloride mixed molten salt solution to 120 ℃, and evaporating redundant HCl and about 90% of free water to obtain the aqueous scandium chloride molten salt, wherein the aqueous scandium chloride molten salt contains NH4Cl, free water and crystal water. And (3) putting the water-containing scandium chloride molten salt into an oven, heating to 110 ℃, preserving heat for 4 hours, and drying to completely remove residual free water and crystal water in the molten salt to obtain the anhydrous scandium chloride molten salt. Finally, the anhydrous scandium chloride molten salt is moved to a tube furnace, and the vacuum degree of the tube furnace is set to be 0.5 multiplied by 10 5 Pa, heating to 500 ℃ at a heating rate of 5 ℃/min, preserving heat for 90 minutes, and removing NH 4 Cl, 16.1g scandium trichloride and scandium oxychloride mixture were finally obtained.
Comparative example 2
Substantially the same as in comparative example 1, except that NH was taken 4 The Cl ammonium source is replaced with an equal amount of aqueous ammonia.
Comparative example 3
Substantially the same as in example 1, except that the heating temperature in step (1) was changed to 70 ℃.
Comparative example 4
Substantially the same as in example 1, except that all of the free water in the scandium trichloride solution was evaporated to dryness in step (2), dry scandium trichloride hexahydrate was obtained.
Characterization test:
the products prepared in the above examples and comparative examples were weighed and calculated in terms of yield, and elemental analysis was performed, and the results are shown in table 1:
TABLE 1
As is clear from Table 1, in each example, the target product anhydrous scandium trichloride was obtained in a yield of 90% or more, and in particular, in a preferred embodiment, it was obtained in a yield of 98% or more. In example 3, since the calcination temperature was low and the calcination time was kept the same as in example 1, there was some tetrahydrofuran residue, resulting in a product containing a certain carbon element, and the yield was low, but the tetrahydrofuran residue could be removed as much as possible by extending the calcination time. In pure anhydrous scandium trichloride, the theoretical mass percent of scandium element is 29.7%, the chlorine element is 70.3%, the ratio of chlorine element to scandium element is about 2.367, the ratio in example 1 is 2.356, the ratio in example 2 is 2.359, the ratio in example 3 is 2.360, the ratio in example 4 is 2.363, the ratio in example 5 is 2.359, the ratio in example 6 is 2.361, all are relatively close to the theoretical value, and the difference between the maximum example 1 and the theoretical value is only 0.5%, so that the purity of anhydrous scandium trichloride prepared in each example is relatively high.
In order to reduce the content of impurity elements as much as possible, the anhydrous scandium trichloride prepared in the conventional method in comparative examples 1 and 2 has avoided the additional introduction of additives such as sodium chloride or potassium chloride in the conventional technology, but the product still has a few impurity element residues, and the ratio of scandium element to chlorine element in the product has too great a difference from the theoretical value, which indicates that the impurity content in the product is very high, and the actual effective yield of scandium trichloride cannot be accurately calculated. In comparative example 3, too low a heating temperature in step (1) resulted in incomplete dissolution of scandium oxide, and the purity of the obtained product was high, but the yield of scandium trichloride was decreased. In comparative example 4, all of the free water in the scandium trichloride solution was evaporated to dryness, resulting in decomposition of scandium trichloride into scandium oxychloride, and the purity of the product was lowered, and the yield could not be precisely calculated.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the application, which are described in detail and are not to be construed as limiting the scope of the application. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. The scope of the application is, therefore, indicated by the appended claims, and the description may be intended to interpret the contents of the claims.
Claims (8)
1. The preparation method of the anhydrous scandium trichloride is characterized by comprising the following steps of:
scandium trichloride hexahydrate, sulfoxide chloride and an organic solvent are mixed and reacted for 10 to 24 hours at the temperature of 15 to 60 ℃, and then the residual organic solvent and sulfoxide chloride are removed by evaporation to prepare a crude product; calcining the crude product in a non-reactive gas atmosphere to prepare anhydrous scandium trichloride;
wherein the organic solvent comprises one or more of tetrahydrofuran, acetonitrile, pyridine, methanol and ethylene glycol dimethyl ether.
2. The production method according to claim 1, wherein the amount of the organic solvent is 2mL or more per 1g of scandium trichloride hexahydrate; and/or
The dosage of the sulfoxide chloride corresponding to each 1g of scandium trichloride hexahydrate is more than or equal to 2mL.
3. The method according to claim 1, wherein the calcination temperature is 400 to 600 ℃, and the calcination time is 2 to 5 hours.
4. The method of claim 1, wherein the evaporating temperature is 40 ℃ to 100 ℃.
5. The production method according to any one of claims 1 to 4, wherein the scandium trichloride hexahydrate is in the form of pasty scandium trichloride hexahydrate containing free water, and the production method of the pasty scandium trichloride hexahydrate comprises the steps of:
scandium oxide is dissolved in a hydrochloric acid aqueous solution to prepare a scandium trichloride solution; heating the scandium trichloride solution at the temperature of 100-180 ℃ to obtain the pasty scandium trichloride hexahydrate.
6. The method according to claim 5, wherein the mass percentage of the free water not combined with scandium trichloride in the pasty scandium trichloride is 3% to 8%.
7. The preparation method according to claim 5, wherein the mass percentage of hydrochloric acid in the aqueous hydrochloric acid solution is 30% -38%.
8. The method according to claim 5, wherein the amount of the aqueous hydrochloric acid solution corresponding to 1g of scandium oxide is 5 to 10mL; and/or
The operation of dissolving scandium oxide in the aqueous solution of hydrochloric acid is carried out at the temperature of 80-150 ℃.
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