CN114920278A - 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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- CN114920278A CN114920278A CN202210596996.1A CN202210596996A CN114920278A CN 114920278 A CN114920278 A CN 114920278A CN 202210596996 A CN202210596996 A CN 202210596996A CN 114920278 A CN114920278 A CN 114920278A
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- Prior art keywords
- scandium
- trichloride
- hexahydrate
- scandium trichloride
- anhydrous
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- DVMZCYSFPFUKKE-UHFFFAOYSA-K scandium chloride Chemical compound Cl[Sc](Cl)Cl DVMZCYSFPFUKKE-UHFFFAOYSA-K 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910001868 water Inorganic materials 0.000 claims abstract description 50
- 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 49
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 40
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000001354 calcination Methods 0.000 claims abstract description 32
- 239000003960 organic solvent Substances 0.000 claims abstract description 31
- 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
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 17
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 17
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001704 evaporation Methods 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000012043 crude product Substances 0.000 claims abstract description 13
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 62
- 239000000243 solution Substances 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 22
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 235000011837 pasties Nutrition 0.000 claims description 8
- 230000008020 evaporation Effects 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000000047 product Substances 0.000 abstract description 20
- 239000013078 crystal Substances 0.000 abstract description 14
- 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
- 230000000052 comparative effect Effects 0.000 description 10
- 235000002639 sodium chloride Nutrition 0.000 description 10
- 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
- 238000005516 engineering process Methods 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 229910052723 transition metal Inorganic materials 0.000 description 7
- 150000003624 transition metals Chemical class 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
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 5
- 238000004090 dissolution 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
- 238000006243 chemical reaction Methods 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
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 241000968352 Scandia <hydrozoan> Species 0.000 description 3
- CJTKCSUNRNSKAD-UHFFFAOYSA-N [Sc].O(Cl)Cl Chemical compound [Sc].O(Cl)Cl CJTKCSUNRNSKAD-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- HJGMWXTVGKLUAQ-UHFFFAOYSA-N oxygen(2-);scandium(3+) Chemical compound [O-2].[O-2].[O-2].[Sc+3].[Sc+3] HJGMWXTVGKLUAQ-UHFFFAOYSA-N 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000010499 C–H functionalization reaction Methods 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
- 230000000996 additive effect 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
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- -1 and in recent years Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 238000003889 chemical engineering 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
- 238000001035 drying 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
- 238000001914 filtration Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000007791 liquid phase Substances 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
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 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
- 238000000746 purification Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- LWIDAIVLBLWUGT-UHFFFAOYSA-N scandium hexahydrate Chemical compound O.O.O.O.O.O.[Sc] LWIDAIVLBLWUGT-UHFFFAOYSA-N 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
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 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 invention 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: mixing scandium chloride hexahydrate, thionyl chloride and an organic solvent, reacting for 10-24 h at 15-60 ℃, and evaporating to remove the residual organic solvent and thionyl chloride 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 to form a stable metal organic complex with a scandium metal center, crystal water in scandium trichloride hexahydrate is replaced, and an introduced organic ligand is removed in a calcining mode, so that high-purity anhydrous scandium trichloride can be prepared. Meanwhile, thionyl chloride which can react with crystal water and generate volatile gas is introduced, so that the purity of the product is further improved.
Description
Technical Field
The invention 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 complex plays a significant role in modern organic synthesis due to the excellent catalytic activity of the transition metal complex. Thanks to the use of transition metal complexes, a large number of completely new catalytic reaction systems are rapidly developed and applied. The precursor of the transition metal complex is often the corresponding anhydrous chloride, so the quality control of the anhydrous chloride is also very important in order to ensure the catalytic performance of the transition metal complex.
The rare earth element scandium is also a transition metal, and in recent years, scandium catalysts gradually show unique activity, regio-and stereoselectivity in the fields of carbon-hydrogen bond activation and the like, and are considered as a transition metal catalyst with development potential because scandium is relatively contained in the earth crust. However, scandium is too dispersed although it is contained in a large amount, which results in a complicated process for extracting and separating scandium. Meanwhile, scandium, 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 high-purity anhydrous scandium trichloride is difficult to prepare in the traditional technology, particularly, the scandium trichloride is easy to hydrolyze in the water removal step, and the preparation process is complex, harsh in conditions and high in risk coefficient, so that the method is not beneficial to industrial production.
Disclosure of Invention
Therefore, the anhydrous scandium trichloride, the preparation method and the application thereof are needed to be provided, the preparation method can avoid scandium trichloride hydrolysis caused by a water removal step in the traditional process, and the prepared anhydrous scandium trichloride is higher in purity and better in quality.
In one aspect of the present invention, a method for preparing anhydrous scandium trichloride is provided, which includes the following steps:
mixing scandium chloride hexahydrate, thionyl chloride and an organic solvent, reacting for 10-24 h at 15-60 ℃, and evaporating to remove the residual organic solvent and thionyl chloride 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 used per 1g of the scandium trichloride hexahydrate is 2mL or more.
In some embodiments, the amount of thionyl chloride used is 2mL or more per 1g of the scandium trichloride hexahydrate.
In some embodiments, the temperature of the calcination is from 400 ℃ to 600 ℃, and the time of the calcination is from 2h to 5 h.
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 paste scandium trichloride hexahydrate containing free water, and the preparation method of the paste scandium trichloride hexahydrate comprises the following steps:
dissolving scandium oxide in hydrochloric acid aqueous solution to prepare scandium trichloride solution; heating the scandium trichloride solution at 100-180 ℃ to obtain the pasty scandium trichloride hexahydrate.
In some embodiments, the paste scandium trichloride hexahydrate contains 3% to 8% by mass of free water not combined with scandium trichloride.
In some embodiments, the hydrochloric acid in the aqueous solution of hydrochloric acid is 30% to 38% by mass.
In some embodiments, the amount of the aqueous hydrochloric acid solution is 5mL to 10mL per 1g of the scandium oxide.
In some embodiments, the dissolving of scandia in aqueous hydrochloric acid is performed at 80 ℃ to 150 ℃.
In another aspect of the present invention, an anhydrous scandium trichloride prepared by the preparation method according to any one of the embodiments is also provided.
In another aspect of the invention, the application of the anhydrous scandium trichloride in preparation of a metal scandium complex is further provided.
According to the invention, a stable metal organic complex is formed with a scandium metal center by introducing organic solvents such as tetrahydrofuran and the like, so that crystal water in scandium trichloride hexahydrate is replaced, and an introduced organic ligand is removed by a calcination mode, so that high-purity anhydrous scandium trichloride can be prepared. Meanwhile, thionyl chloride which can react with crystal water and generate volatile gas is introduced, so that coordination of an organic solvent and a metal center can be promoted, the residual of water can be reduced, and the purity of the product is further improved. The problem that the purity of the product is reduced due to the fact that scandium trichloride is easy to hydrolyze due to dehydration in the traditional technology or introduced additives are not easy to remove is effectively solved. In addition, the preparation method is simple to operate and easy for industrial production, and avoids the adoption of harsh, complex, dangerous and environmentally-friendly preparation processes such as chlorine calcination and the like in the traditional technology.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the accompanying examples. This invention 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 "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the invention, "a plurality" means at least two, e.g., two, three, etc., unless explicitly specified otherwise. In the description of the present invention, "a plurality" means at least one, e.g., one, two, etc., unless specifically limited 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 invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In the present invention, the technical features described in the open type include a closed technical solution composed of the listed features, and also include an open technical solution including the listed features.
In the present invention, the numerical intervals are regarded as continuous, and include the minimum and maximum values of the range 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-describing 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 encompass any and all subranges subsumed therein.
The percentage contents referred to in the present invention mean, unless otherwise specified, mass percentages for solid-liquid mixing and solid-solid phase mixing, and volume percentages for liquid-liquid phase mixing.
The percentage concentrations referred to in the present invention are, unless otherwise specified, the final concentrations. The final concentration refers to the ratio of the additive component in the system to which the component is added.
The temperature parameter in the present invention is not particularly limited, and may be a constant temperature treatment or a treatment within a certain temperature range. The constant temperature process allows the temperature to fluctuate within the accuracy of the instrument control.
In the present invention, "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) scandium oxide is refluxed and dissolved in hydrochloric acid aqueous solution, then ammonium hydroxide solution is added, after heating and boiling for removing water, the obtained wet solid is dried overnight at room temperature in vacuum, and then further water removal and purification are carried out through step-by-step calcination, but the yield of the method can only reach about 64% 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 in an argon protective atmosphere after the reaction is finished to obtain an anhydrous scandium trichloride crystal with larger granularity; (3) slowly heating and melting aluminum chloride and scandium oxide at 220-280 ℃, then heating to over 500 ℃ for calcining, and removing redundant aluminum trichloride; (4) mixing a mixed solution of sodium chloride, potassium chloride and ammonium chloride with a scandium oxide solution dissolved in 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 the vacuum condition of about 500 ℃ to remove 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 and have low yield and purity, or require harsh conditions such as calcination in a chlorine atmosphere at 900 ℃, or require the introduction of aluminum, sodium, potassium and other miscellaneous elements that are difficult to remove, and in short, it is difficult to obtain high-purity anhydrous scandium trichloride by a relatively simple and industrially easy preparation process.
Based on the above background, the present inventors have conducted extensive studies to provide a method for producing anhydrous scandium trichloride, which includes the steps of:
mixing scandium chloride hexahydrate, thionyl chloride and an organic solvent, reacting for 10-24 hours at 15-60 ℃, and evaporating to remove the residual organic solvent and thionyl chloride 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 to form a stable metal organic complex with a scandium metal center, crystal water in scandium chloride hexahydrate is replaced, and an introduced organic ligand is removed in a calcining mode, so that high-purity anhydrous scandium chloride can be prepared. Meanwhile, thionyl chloride which can react with crystal water and generate volatile gas is introduced, so that coordination of an organic solvent and a metal center can be promoted, the residual of water can be reduced, and the purity of the product is further improved. The method effectively solves the problem that in the prior art, scandium trichloride is easy to hydrolyze due to dehydration, or introduced additives are not easy to remove, so that the product purity is reduced. In addition, the preparation method is simple to operate and easy for industrial production, and avoids the adoption of harsh, complex, dangerous and environmentally-friendly preparation processes such as chlorine calcination and the like in the traditional technology.
Preferably, the organic solvent is one or more of tetrahydrofuran, methanol and acetonitrile.
Further preferably, the organic solvent is tetrahydrofuran, 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 the scandium trichloride hexahydrate, and the volatilization or decomposition of reaction raw materials cannot be caused.
In some embodiments, the reaction time may also be 12h, 14h, 16h, 18h, 20h, or 22h, for example. Preferably, the reaction time is 10h to 14 h. The appropriate reaction time enables the organic solvent to be completely coordinated with the metallic scandium center and avoids the occurrence of side reactions.
In some embodiments, the amount of organic solvent used per 1g of scandium trichloride hexahydrate is 2mL or more. The amount of the organic solvent to be used per 1g of scandium trichloride hexahydrate may be, for example, 4mL, 6mL, 8mL, 10mL, 12mL, 14mL or 16 mL. Preferably, the dosage of the organic solvent is 2 mL-10 mL per 1g of scandium trichloride hexahydrate. The appropriate amount of the organic solvent can enable the crystallized water in the scandium trichloride hexahydrate to be replaced completely and be removed more easily subsequently.
In some embodiments, the amount of thionyl chloride per 1g of scandium trichloride hexahydrate is 2mL or more. The amount of thionyl chloride per 1g of scandium trichloride hexahydrate may be, for example, 4mL, 6mL, 8mL, 10mL, 12mL, 14mL or 16 mL. Preferably, the dosage of the thionyl chloride corresponding to 1g of scandium trichloride hexahydrate is 2 mL-10 mL. The proper amount of the thionyl chloride can help to remove crystal water in the scandium trichloride hexahydrate, so that a metal center is more easily coordinated with an organic solvent, the purity of the product is further improved, and the product is easier to remove subsequently.
In the above-mentioned "… … for every 1g of scandium trichloride hexahydrate", the phrase "every 1g of scandium trichloride hexahydrate" means that the mass of pure scandium trichloride hexahydrate is 1g, and the mass of other components is not included. For example, if it is mentioned later that "the form of scandium trichloride hexahydrate is paste-like scandium trichloride hexahydrate containing free water", then the total mass of scandium trichloride hexahydrate containing free water should be calculated and taken based on the mass of scandium trichloride hexahydrate being 1g and the mass percentage content of free water in scandium trichloride paste-like scandium hexahydrate, and the scandium trichloride paste-like six hydrate cannot be taken out directly according to the mass of 1 g.
In some embodiments, the temperature of calcination is from 400 ℃ to 600 ℃ and the time of calcination is from 2h to 5 h. Preferably, the temperature of calcination is from 500 ℃ to 550 ℃. The temperature of the calcination may be, for example, 420 ℃, 440 ℃, 460 ℃, 480 ℃, 500 ℃, 520 ℃, 540 ℃, 560 ℃ or 580 ℃. The calcination time can also be, for example, 3h or 4 h. The proper calcining temperature and calcining time can completely remove the tetrahydrofuran combined with the scandium metal center, avoid the residue of the impurity elements and cannot cause the 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 proper evaporation temperature can completely remove the redundant organic solvent and thionyl chloride without causing bumping.
In some embodiments, the scandium trichloride hexahydrate is in the form of a paste scandium trichloride hexahydrate containing free water, and the method for preparing the paste scandium trichloride hexahydrate comprises the following steps:
dissolving scandium oxide in hydrochloric acid aqueous solution to prepare scandium trichloride solution; heating the scandium trichloride solution at 100-180 ℃ to obtain pasty scandium trichloride hexahydrate. The scandium trichloride solution is heated to be pasty, a certain amount of free water is reserved, the scandium trichloride can be prevented from being hydrolyzed to generate scandium oxychloride due to the fact that all water is evaporated to dryness, and the product purity is reduced.
Preferably, the heating temperature of the scandium trichloride solution is 120 ℃ to 150 ℃. The proper heating temperature can lead the water removal time to be faster, and can not cause bumping, and the water removal amount is difficult to control. The heating temperature may also be 140 ℃ or 160 ℃, for example.
In some embodiments, the paste scandium trichloride hexahydrate contains 3% to 8% by mass of free water not bound to scandium trichloride. The free water may also be present in an amount of, for example, 4%, 5%, 6% or 7% by mass. Controlling the content of free water in a proper range does not lead to the hydrolysis of scandium trichloride, and can ensure that crystal water in scandium trichloride hexahydrate can be completely replaced by an organic solvent in a subsequent step.
In some embodiments, the hydrochloric acid in the aqueous solution is 30% to 38% by weight. The hydrochloric acid may be contained in the aqueous hydrochloric acid solution in an amount of, for example, 32%, 34% or 36% by mass. The appropriate hydrochloric acid concentration enables the scandium oxide to be dissolved more thoroughly. Preferably, electronic grade aqueous hydrochloric acid is used to further reduce impurity incorporation.
In some embodiments, the amount of aqueous hydrochloric acid used is 5mL to 10mL per 1g of scandia. The amount of the aqueous hydrochloric acid solution to be used per 1g of scandium oxide may be, for example, 6mL or 8 mL. The appropriate amount of aqueous hydrochloric acid can be used to dissolve scandium oxide completely and remove it more easily.
In some embodiments, the dissolving of scandia in aqueous hydrochloric acid is performed at 80 ℃ to 150 ℃. Preferably, the scandium oxide is dissolved in the aqueous hydrochloric acid solution at 100 to 120 ℃. The temperature at which the scandium oxide is dissolved in the aqueous hydrochloric acid solution may be, for example, 90 ℃, 110 ℃ or 130 ℃. The dissolution temperature is related to the dissolution degree and dissolution rate of scandium oxide, and improper setting of the temperature can cause incomplete dissolution of scandium oxide, introduce impurities and reduce the yield.
In another aspect of the present invention, an anhydrous scandium trichloride prepared by the preparation method according to any one of the embodiments is also provided. Compared with the anhydrous scandium trichloride prepared by the traditional technology, the anhydrous scandium trichloride prepared by the preparation method has higher purity and less impurity elements.
In another aspect of the present invention, an application of the anhydrous scandium trichloride in preparation of a metal scandium complex is also provided.
The present invention will be described in further detail with reference to specific examples and comparative examples. Experimental parameters not described in the following specific examples are preferably referred to the guidelines given in the present application, and may be referred to experimental manuals in the art or other experimental methods known in the art, or to experimental conditions recommended by the manufacturer. It is understood that the following examples are specific to the particular apparatus and materials used, and in other embodiments, are not limited thereto; the weight of the related components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight of each component, therefore, the proportional enlargement or reduction of the content of the related components according to the description of the embodiments of the present invention is within the scope disclosed in the embodiments of the present invention. Specifically, the weight described in the description of the embodiment of the present invention may be a mass unit known in the chemical engineering field such as μ g, mg, g, kg, etc.
Example 1
(1) Weighing 4.8g of scandium oxide, and dissolving in 35mL of concentrated hydrochloric acid (38 wt% hydrochloric acid aqueous solution) under the heating condition of 110 ℃ to obtain a clear scandium chloride solution;
(2) heating and evaporating the clarified 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 trichloride hexahydrate with the free water content of about 5% by mass;
(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 remains to obtain a crude product;
(4) and (4) calcining the crude product prepared in the step (3) for 3 hours at 500 ℃ in a dry argon atmosphere to obtain an anhydrous scandium trichloride product.
Example 2
(1) Weighing 4.2g of scandium oxide, and dissolving in 35mL of concentrated hydrochloric acid (38 wt% hydrochloric acid aqueous solution) under the heating condition of 110 ℃ to obtain a clear scandium chloride solution;
(2) heating and evaporating the clarified 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 trichloride hexahydrate with the free water content of about 5% by mass;
(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 to obtain a crude product;
(4) and (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 an equal volume of acetonitrile.
Example 5
Substantially the same as in example 1 except that tetrahydrofuran in step (3) was changed to an equal volume of methanol.
Example 6
Substantially the same as in example 1 except that tetrahydrofuran in step (3) was replaced with an equal volume of pyridine.
Comparative example 1
10g of scandium oxide having a purity of 99.0% was dissolved in 50mL of 30% hydrochloric acid at a heating temperature of 90 ℃ to prepare a scandium chloride solution. Configuration of NH 4 Cl solution, then adding scandium chloride solution and NH 4 Mixing with Cl solution containing scandium chloride and NH 4 The mass ratio of Cl is 1: and 3, filtering residues after stirring to obtain a scandium chloride mixed molten salt solution. Heating the prepared scandium chloride mixed molten salt solution to 120 ℃, and evaporating redundant HCl and about 90% of free water to obtain hydrous scandium chloride molten saltThe scandium-melting 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 the temperature for 4 hours, and drying to completely remove the 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 tubular furnace, and the vacuum degree of the tubular furnace is set to be 0.5 multiplied by 10 5 Pa, heating rate of 5 deg.C/min to 500 deg.C, maintaining for 90 min, and removing NH 4 Cl, 16.1g of a scandium trichloride and scandium oxychloride mixture was finally obtained.
Comparative example 2
Substantially the same as in comparative example 1 except that NH was added 4 The Cl ammonium source was replaced with ammonia in equal amounts.
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 in step (2), the free water in the scandium trichloride solution was completely evaporated to dryness to obtain dried scandium trichloride hexahydrate.
Characterization test:
the products obtained in the above examples and comparative examples were weighed and yield-calculated, and subjected to elemental analysis, and the results are shown in table 1:
TABLE 1
As is clear from table 1, the target product, namely, anhydrous scandium trichloride, can be obtained in a yield of 90% or more in each example, and particularly, in a preferable embodiment, it can be obtained in a yield of 98% or more. In example 3, since the calcination temperature was low and the calcination time was consistent with that of example 1, some tetrahydrofuran remained, resulting in a product containing a certain amount of carbon element, and the yield was low, but the tetrahydrofuran remained 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 theoretical mass percent of chlorine element is 70.3%, the ratio of chlorine element/scandium element is about 2.367 in example 1, the ratio is 2.356 in example 2, the ratio is 2.359 in example 2, the ratio is 2.360 in example 3, the ratio is 2.363 in example 4, the ratio is 2.359 in example 5, and the ratio is 2.361 in example 6, which are both close to the theoretical value, and the largest difference between example 1 and the theoretical value is only 0.5%, so that the purity of the anhydrous scandium trichloride prepared in each example is high.
Comparative examples 1 and 2 are both anhydrous scandium trichloride prepared by the conventional method, in order to reduce the content of impurity elements as much as possible, the additional introduction of additives such as sodium chloride or potassium chloride in the conventional technology is avoided, but a lot of impurity elements remain in the product, and the ratio of scandium element and chlorine element in the product is too large different from the theoretical value, which indicates that the content of impurity 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 although the product obtained was of higher purity, it resulted in a decrease in the yield of scandium trichloride. In comparative example 4, the free water in the scandium trichloride solution was completely evaporated to dryness, which resulted in decomposition of scandium trichloride into scandium oxychloride, and the product purity decreased, and the yield could not be accurately calculated.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the patent of the invention is subject to the appended claims, and the description can be used for explaining the contents of the claims.
Claims (10)
1. The preparation method of anhydrous scandium trichloride is characterized by comprising the following steps:
mixing scandium chloride hexahydrate, thionyl chloride and an organic solvent, reacting for 10-24 h at 15-60 ℃, and evaporating to remove the residual organic solvent and thionyl chloride 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 preparation method according to claim 1, wherein the amount of the organic solvent used per 1g of the scandium trichloride hexahydrate is 2mL or more; and/or
The dosage of the thionyl chloride corresponding to every 1g of the scandium trichloride hexahydrate is more than or equal to 2 mL.
3. The preparation method according to claim 1, wherein the calcination temperature is 400-600 ℃, and the calcination time is 2-5 h.
4. The method of claim 1, wherein the temperature of the evaporation is 40 ℃ to 100 ℃.
5. The method according to any one of claims 1 to 4, wherein the scandium trichloride hexahydrate is in the form of a paste-like scandium trichloride hexahydrate containing free water, and the method for producing the scandium trichloride hexahydrate comprises the steps of:
dissolving scandium oxide in hydrochloric acid aqueous solution to prepare scandium trichloride solution; heating the scandium trichloride solution at 100-180 ℃ to obtain the pasty scandium trichloride hexahydrate.
6. The method according to claim 5, wherein the paste-like scandium trichloride hexahydrate comprises, by mass, 3% to 8% of free water not combined with scandium trichloride.
7. The preparation method according to claim 5, wherein the hydrochloric acid is contained in the aqueous solution of hydrochloric acid in an amount of 30 to 38% by mass.
8. The method according to claim 5, wherein the amount of the aqueous hydrochloric acid solution is 5 to 10mL per 1g of the scandium oxide; and/or
The scandium oxide is dissolved in the hydrochloric acid aqueous solution at 80-150 ℃.
9. An anhydrous scandium trichloride, which is produced by the production method according to any one of claims 1 to 8.
10. Use of anhydrous scandium trichloride as claimed in claim 9 for preparing a metal scandium complex.
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