CN101254942B - Method for preparing high-purity anhydrous indium trichloride - Google Patents
Method for preparing high-purity anhydrous indium trichloride Download PDFInfo
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- CN101254942B CN101254942B CN2008100582505A CN200810058250A CN101254942B CN 101254942 B CN101254942 B CN 101254942B CN 2008100582505 A CN2008100582505 A CN 2008100582505A CN 200810058250 A CN200810058250 A CN 200810058250A CN 101254942 B CN101254942 B CN 101254942B
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- Prior art keywords
- indium
- chloride
- propyl carbinol
- anhydrous
- incl
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- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims description 26
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000004821 distillation Methods 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 229910052738 indium Inorganic materials 0.000 claims abstract description 14
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 14
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000018044 dehydration Effects 0.000 claims abstract description 8
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 8
- 238000000746 purification Methods 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000859 sublimation Methods 0.000 claims abstract description 6
- 230000008022 sublimation Effects 0.000 claims abstract description 6
- 229910021617 Indium monochloride Inorganic materials 0.000 claims description 27
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 claims description 27
- 229940055742 indium-111 Drugs 0.000 claims description 22
- 239000013078 crystal Substances 0.000 claims description 19
- APFVFJFRJDLVQX-AHCXROLUSA-N indium-111 Chemical compound [111In] APFVFJFRJDLVQX-AHCXROLUSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 230000036571 hydration Effects 0.000 claims description 8
- 238000006703 hydration reaction Methods 0.000 claims description 8
- 235000011837 pasties Nutrition 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- -1 Indium-111 chlorides Chemical class 0.000 claims description 6
- LMSNZLCSZWZZGU-UHFFFAOYSA-N butan-1-ol;hydrochloride Chemical compound Cl.CCCCO LMSNZLCSZWZZGU-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 abstract description 10
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000005660 chlorination reaction Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000004411 aluminium Substances 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
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000002061 vacuum sublimation Methods 0.000 description 1
Abstract
The invention relates to a preparation method of high purity anhydrous indium trichloride, which belongs to the technology field of rare metal fine chemical industry. The preparation method includes:Using 99.99-99.999% Indium metal and 36% hydrochloric acid as the material and using organic solvents including n-butyl alcohol and n-heptane as the dehydrant, that is, using more unstable complex toreplace more stable compound, the stable hydrated indium trichloride is replaced with the more unstable complex of the indium trichloride organic solvent; adopting a manner of microwave heating and gradually heating up including three steps of distillation dehydration at normal pressure, distillation de-reagent at reduced pressure and sublimation and purification of the anhydrous indium trichloride; and finally obtaining the high purity anhydrous indium trichloride (InCl3), which is white with a purity of up to 99.99-99.999% and a production rate of 97%-98%.
Description
One, technical field: the present invention relates to a kind of method for preparing high-purity anhydrous indium trichloride, belong to rare metal fine chemical technology field.
Two, background technology
High-purity anhydrous indium trichloride (InCl
3) be the main raw material of preparation ito thin film and III-V family semiconductor material, it is one of important solar cell material, also be the basic raw material of synthetic organo indium series compound, can be used as the catalyzer of organic reaction, have application widely aspect organic synthesis, the electronic industry.China is indium resource big country, and annual metal smelting indium can reach 400 tons, occupies first place in the world.But InCl
3Production at present domesticly only can produce InCl
34H
2O and InCl
3, and high-pure anhydrous InCl
3Necessary import costs an arm and a leg.Though prepare anhydrous InCl
3Method many, decompose chlorination process and hydrate thermal dehydration method, organic solvent method, the chlorination process etc. that heats up progressively as indium metal direct chlorination method, oxide compound.Optimum temps with the indium metal direct chlorination is 430 ℃, when heating carefully and feed the chlorine that is fit to, can generate vaporific Indium-111 chloride; Also available tetracol phenixin and Indium sesquioxide react and make Indium-111 chloride; Can also work with thionyl chloride and Indium sesquioxide one, excessive reagent be boiled off to obtain anhydrous indium chloride.In addition, adopting the chlorination process that progressively heats up, is raw material with In, and the chlorination that progressively heats up is Indium-111 chloride, feeds rare gas element and makes the protection gas cooling and make.Wu Shihua adopts the chlorination process that progressively heats up to synthesize anhydrous indium chloride.The purification of Indium-111 chloride generally is to adopt to be placed on cl gas flow or indifferent gas (N
2, Ar, CO
2) method of carrying out one or many distillation in stream or both blended air-flows.Also can adopt the method for vacuum-sublimation, muriate and other the volatile impurity in order to dispose aluminium, iron (III) simultaneously is heated to reactant about 300 ℃ and gets final product in inert gas.Also can adopt organic solvent method purification Indium-111 chloride, because InCl
34H
2H among the O
2The polar organic solvent that O can be had oxygen, nitrogen donor replaces, thus Zhou Zhihua etc. with propyl carbinol BuOH as organic solvent, adopt organic solvent method with InCl
34H
2The O dehydration has prepared anhydrous indium chloride.These preparation methods respectively have relative merits, and certain methods is that the raw material reagent purity is had relatively high expectations, and are comparatively strict to temperature control, and equipment complexity, output are lower, certain methods be aftertreatment be difficult to and environmental pollution serious etc.Though existing abroad bibliographical information utilizes organic solvents such as amine, methane amide and kerosene to slough crystal water in the crystallization muriate with the preparation anhydrous chloride, but also because the related process of these reactions more complicated often, long reaction time, requirement for experiment condition are higher, the reagent costliness, exist organic reagent contamination and comparison danger, equipment volume big, the energy consumption height, not easy to operate, resource is few, the high difficulty of cost.
Three, summary of the invention
The object of the present invention is to provide a kind of method for preparing high-purity anhydrous indium trichloride.With the indium metal (In) of 99.99%-99.999% and 36% hydrochloric acid (HCl) is raw material, with organic solvent propyl carbinol, normal heptane is dewatering agent, promptly replace more stable compound with more unsettled title complex, the stable crystal water Indium-111 chloride that contains is replaced to more unsettled Indium-111 chloride organic solvent title complex, adopt progressively temperature-raising method of microwave heating then, take off reagent, three links of anhydrous indium chloride sublimation purification through normal pressure distillation dehydration, underpressure distillation, finally make white, purity reaches the high-purity anhydrous indium trichloride (InCl of 99.99%-99.999%
3), its productive rate reaches 97%-98%.
The present invention finishes according to the following steps
(1) indium metal (In) of raw material 99.99～99.999% being added concentration expressed in percentage by weight is that control In and HCl mol ratio are 1: 2～4, are warming up to 30-55 ℃, continue stirring until indium metal and dissolve fully, obtain InCl in 36% the hydrochloric acid (HCl)
3The aqueous solution; With aqueous solution evaporate, get four hydration Indium-111 chloride (InCl
34H
2O) white crystal; In crystal, add organic dewatering agent, in microwave oven, controlled temperature 90-120 ℃, carry out the air distillation dehydration, obtain pasty state Indium-111 chloride propyl carbinol title complex or unsettled Indium-111 chloride propyl carbinol and normal heptane mixed ligand complex (InCl
3MBuOH),
Described organic dewatering agent is propyl carbinol (BuOH), the weight ratio (BuOH/H of contained crystal water in propyl carbinol and the four hydration Indium-111 chlorides
2O) be 35-45, or the ratio of propyl carbinol and normal heptane be 1: 1 mixture, the weight ratio of contained crystal water is 25-35 in propyl carbinol+normal heptane mixture and the four hydration Indium-111 chlorides;
(2) with pasty state title complex (InCl
3MBuOH), in microwave oven, 130～280 ℃ of controlled temperature, vacuum tightness is 6-10kPa, distillation 5-10min carries out underpressure distillation and removes organic dewatering agent, obtains white plates anhydrous indium chloride (InCl
3);
(3) with anhydrous indium chloride (InCl
3) in microwave oven, 300～400 ℃ of following sublimation purification 5-10min of controlled temperature obtain the high-purity anhydrous indium trichloride (InCl that white fluffy needle-like has metalluster
3) crystal product.
Compare advantage and positively effect that the present invention has with known technology
(1) adopt microwave heating progressively temperature-raising method prepare high-purity anhydrous indium trichloride, the time is short, the productive rate height, pollute few, good product quality.Overcome that high temperature prepares Indium-111 chloride process complexity in the ordinary method, power consumption height, shortcoming such as the time is long, cost is high, technical process is long.Solve solvent in the organic solvent desiccating method and can't reuse problem and the rotten problem of high-temperature product.
(2) selected organic dewatering agent makes reactant InCl
34H
2O solubleness therein is bigger; Solvent can separate water outlet effectively and be easy to recovery; Solvent is to InCl
3Better chemical stability is arranged, and promptly side reaction is minimum; Reaction product not with solvent action; Solvent is easy to separate with product; Little, the pollution-free and low price of this solvent toxicity.
Four, embodiment
Embodiment 1: getting 99.99% pure metal indium (In) 11.48g, to add concentration expressed in percentage by weight be 36% hydrochloric acid (HCl) 50ml, is warming up to 45 ℃, continues stirring until indium metal and dissolve fully and obtain InCl
3The aqueous solution gets four hydration Indium-111 chloride (InCl with aqueous solution evaporate
34H
2O) white crystal; In crystal, add propyl carbinol (BuOH) 245ml, the ratio (BuOH/H of its propyl carbinol and crystal water
2O) be 35, under the condition of 100 ℃ of temperature, carry out the air distillation dehydration, obtain pasty state product Indium-111 chloride propyl carbinol title complex (InCl
3MBuOH); Temperature is risen to 180 ℃, to pasty state title complex (InCl
3MBuOH) carry out underpressure distillation 10min, vacuum tightness is 8kPa, obtains anhydrous indium chloride (InCl
3); At this moment temperature is risen to 350 ℃ to anhydrous indium chloride (InCl
3) carry out sublimation purification 10min, obtain the high-purity anhydrous indium trichloride (InCl that white fluffy needle-like has metalluster
3) crystal product.Its purity reaches 99.9958%, and productive rate reaches 97%.
Embodiment 2: getting 99.99% pure metal indium (In) 11.48g, to add concentration expressed in percentage by weight be 36% hydrochloric acid (HCl) 50ml, is warming up to 45 ℃, continues stirring until indium metal and dissolve fully, obtains InCl
3The aqueous solution with its aqueous solution evaporate, gets four hydration Indium-111 chloride (InCl
34H
2O) white crystal; The mixture that adds propyl carbinol 105ml and normal heptane 105ml in crystal under the condition of 95 ℃ of temperature, carries out the air distillation dehydration, obtains unsettled Indium-111 chloride of pasty state and propyl carbinol and normal heptane mixed ligand complex (InCl
3MBuOH); With pasty state title complex (InCl
3MBuOH), at 150 ℃ of following underpressure distillation 8min of temperature, vacuum tightness is 8kPa, obtains white plates anhydrous indium chloride (InCl
3); With anhydrous indium chloride (InCl
3) at 350 ℃ of following sublimation purification 10min of temperature, obtain the high-purity anhydrous indium trichloride (InCl that white fluffy needle-like has metalluster
3) crystal product.Its purity reaches 99.9974%, and productive rate reaches 98%.
Claims (1)
1. method for preparing high-purity anhydrous indium trichloride, it is that control In and HCl mol ratio are 1: 2～4, are warming up to 30-55 ℃ in 36% the hydrochloric acid that the indium metal of raw material 99.99～99.999% is added concentration expressed in percentage by weight, continue stirring until indium metal and dissolve fully, obtain InCl
3The aqueous solution; With aqueous solution evaporate, get four hydration Indium-111 chloride white crystals; In crystal, add organic dewatering agent, described organic dewatering agent be propyl carbinol or propyl carbinol with the ratio of normal heptane be 1: 1 mixture, in microwave oven, controlled temperature 90-120 ℃, carry out the air distillation dehydration, obtain pasty state Indium-111 chloride propyl carbinol title complex or unsettled Indium-111 chloride propyl carbinol and normal heptane mixed ligand complex; With the pasty state title complex, in microwave oven, 130～280 ℃ of controlled temperature, vacuum tightness is 6-10kPa, distillation 5-10min carries out underpressure distillation and removes organic dewatering agent, obtains the white plates anhydrous indium chloride; In microwave oven, 300～400 ℃ of following sublimation purification 5-10min of controlled temperature obtain the high-purity anhydrous indium trichloride crystal product that white fluffy needle-like has metalluster with anhydrous indium chloride,
It is characterized in that: the weight ratio of contained crystal water is 35-45 in propyl carbinol and the four hydration Indium-111 chlorides, and the weight ratio of contained crystal water is 25-35 in propyl carbinol and normal heptane mixture and the four hydration Indium-111 chlorides.
Priority Applications (1)
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|---|---|---|---|
| CN2008100582505A CN101254942B (en) | 2008-04-07 | 2008-04-07 | Method for preparing high-purity anhydrous indium trichloride |
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|---|---|---|---|
| CN2008100582505A CN101254942B (en) | 2008-04-07 | 2008-04-07 | Method for preparing high-purity anhydrous indium trichloride |
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| CN101254942A CN101254942A (en) | 2008-09-03 |
| CN101254942B true CN101254942B (en) | 2010-06-02 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101792174B (en) * | 2010-03-12 | 2012-07-04 | 韶关市锦源实业有限公司 | Anhydrous indium chloride synthesizing method |
| CN104129817B (en) * | 2014-06-27 | 2016-04-20 | 济南大学 | A kind of solvent displacement prepares the method for waterless cobaltous chloride |
| CN106517309A (en) * | 2016-11-11 | 2017-03-22 | 清华大学 | High density indium oxide and preparation method thereof |
| CN107226480B (en) * | 2017-06-23 | 2019-01-22 | 慕平 | A method of anhydrous indium salts and anhydrous pink salt are recycled from tin indium oxide |
| CN107285372A (en) * | 2017-08-11 | 2017-10-24 | 广东先导稀材股份有限公司 | The preparation method of indium trichloride |
| CN109775747B (en) * | 2019-04-03 | 2020-05-08 | 云南锡业集团（控股）有限责任公司研发中心 | Preparation method of high-purity anhydrous indium trichloride |
| CN112299473A (en) * | 2020-11-23 | 2021-02-02 | 清远先导材料有限公司 | Preparation system and method of high-purity indium trichloride |
Citations (3)
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|---|---|---|---|---|
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| CN1613770A (en) * | 2004-07-24 | 2005-05-11 | 陈瑜 | Process for producing anhydrous magnesium chloride by microwave energy |
| CN101033079A (en) * | 2006-12-12 | 2007-09-12 | 云南锡业集团（控股）有限责任公司 | Process of preparing anhydrous indium chloride |
-
2008
- 2008-04-07 CN CN2008100582505A patent/CN101254942B/en not_active Expired - Fee Related
Patent Citations (3)
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|---|---|---|---|---|
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| CN1613770A (en) * | 2004-07-24 | 2005-05-11 | 陈瑜 | Process for producing anhydrous magnesium chloride by microwave energy |
| CN101033079A (en) * | 2006-12-12 | 2007-09-12 | 云南锡业集团（控股）有限责任公司 | Process of preparing anhydrous indium chloride |
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