CN102502757B - Method for preparing high-purity anhydrous lanthanum chloride or cerium chloride by programmed heating method - Google Patents
Method for preparing high-purity anhydrous lanthanum chloride or cerium chloride by programmed heating method Download PDFInfo
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- CN102502757B CN102502757B CN 201110346254 CN201110346254A CN102502757B CN 102502757 B CN102502757 B CN 102502757B CN 201110346254 CN201110346254 CN 201110346254 CN 201110346254 A CN201110346254 A CN 201110346254A CN 102502757 B CN102502757 B CN 102502757B
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Abstract
The invention relates to preparation method of high-purity anhydrous lanthanum chloride or cerium chloride by a programmed heating method, and belongs to the field of preparation of rare-earth materials. LaCl3.7H2O or CeCl3.7H2O and ammonium chloride are mixed in a weight ratio of 4:1, and vacuumizing is performed by using a water jet pump; when the vacuum degree reaches 0.08Pa, a heating program is set for heating at the temperature of between room temperature and 360 DEG C, and the sectional heating speed and the heat preservation time are controlled; by analysis and detection, the water content of the obtained anhydrous lanthanum chloride or cerium chloride is less than 0.1 percent; and the anhydrous lanthanum chloride or cerium chloride is immediately dissolved when added into water, the aqueous solution obtained after the anhydrous lanthanum chloride or cerium chloride is dissolved is clear and transparent, and the purity of the product is over 99.9 percent. The method has already been applied to a production line capable of producing 100 kilograms of anhydrous lanthanum chloride or cerium chloride in each batch in an industrial-scale programmed heating furnace.
Description
Technical field
The present invention relates to a kind ofly prepare the method for high-pure anhydrous Lanthanum trichloride or Cerium II Chloride by programmed temperature method, belong to the rare earth material preparation field.
Background technology
High-pure anhydrous Lanthanum trichloride and Cerium II Chloride can be respectively applied to the preparation of scintillator crystal materials, organic catalyst compound, high-purity lanthanum or cerium metal, the Application Areass such as reaction of rare earth non-aqueous solution.Anhydrous lanthanum chloride or Cerium II Chloride preparation method have chloride monohydrate evaporation and oxide compound chlorination process etc.Chinese patent 200610067759.7 discloses " the chloridizing roasting evaporation preparation technology of anhydrous lanthanum chloride ", and this method is with LaCl
37H
2O is raw material, in chloridizing roasting processed process, keep feeding the capacity dry hydrogen chloride gas, maturing temperature is controlled in 200～300 ℃, prepare the anhydrous lanthanum chloride of higher degree, this method hydrogen chloride gas in industrial-scale production is more serious to equipment corrosion, needs simultaneously tail gas is carried out intensive treatment.Beautiful " the anhydrous rare-earth chlorination cerium Study on Preparation " of showing of document Wu, the process engineering journal, 2011,11 (1): 103-106, a kind of anhydrous cerium chloride preparation method is provided, containing insolubless such as CeOCl in the anhydrous cerium chloride is 3.94%; " vacuum dehydration method prepares the research of anhydrous cerium chloride " that document Han Ji dragon is shown, inorganic chemicals industry, 2009,41 (10): 25-26 provides a kind of CeCl
37H
2O and ammonium chloride are blended under the vacuum condition dehydration, and to obtain anhydrous cerium chloride purity be 93%; Chinese patent 200510132520.9 discloses " preparation method of anhydrous cerium chloride ", and this method is with CeCl
37H
2O and ammonium chloride mix, and are thermal dehydration under 120 ℃-370 ℃ the condition in temperature, and the anhydrous cerium chloride water content that obtains is less than 2%, and water-insoluble is less than 1%; The anhydrous cerium chloride water content height that these preparation methods obtain, also contain water-insoluble simultaneously, can't use in fields such as scintillator crystal materials, organic catalyst compounds.Scintillator crystal materials and organic catalyst compound require the dissolving that is added to the water at once of high-pure anhydrous Lanthanum trichloride or Cerium II Chloride, and the dissolving rear solution is limpid transparent, can not contain water-insoluble, and high-pure anhydrous Lanthanum trichloride and Cerium II Chloride water content all require less than 0.1%.
Summary of the invention
The purpose of this invention is to provide a kind of method that is prepared high-pure anhydrous Lanthanum trichloride or Cerium II Chloride by programmed temperature method, this method obtains high-pure anhydrous Lanthanum trichloride or Cerium II Chloride product in technical scale, wherein water content is less than 0.1%, product is added to the water and dissolves at once, the dissolving rear solution is limpid transparent, product purity is greater than 99%, and yield is greater than 99%.
Technical solution: will directly separate Lanthanum trichloride or the solution of cerium chloride by oxidation heating condensing crystal of preparing from rare earth extraction, and obtain particulate state crystal LaCl
37H
2O or CeCl
37H
2O contains lanthanum trioxide or cerium oxide purity greater than 99.99%, LaCl in the rare earth oxide amount
37H
2O or CeCl
37H
2O and ammonium chloride mixed in mixer by weight 4: 1, it is in 1 liter of porcelain alms bowl that mixed material is respectively charged into volume, the porcelain alms bowl that will contain material is more evenly put in the temperature programming stove, vacuumize with water jet pump, when vacuum tightness reaches 0.08Pa, set heating schedule and begin heating, heating schedule is: room temperature～120 ℃, heat-up rate is 0.83 ℃/minute, and 2 hours heating-up times were 120 ℃ of soaking times 4 hours; 120 ℃～240 ℃, heat-up rate is 2 ℃/minute, and 1 hour heating-up time was 240 ℃ of soaking times 4 hours; 240 ℃～300 ℃, heat-up rate is 0.5 ℃/minute, and 2 hours heating-up times were 300 ℃ of soaking times 2 hours; 300 ℃～360 ℃, heat-up rate is 0.5 ℃/minute, 2 hours heating-up times are 360 ℃ of soaking times 7～7.3 hours, when furnace body temperature drops to 50 ℃ naturally, discharging, vacuum packaging, the anhydrous lanthanum chloride that obtains or Cerium II Chloride detect water content by analysis less than 0.1%, and dissolving at once is added to the water, the dissolving rear solution is limpid transparent, and product purity is greater than 99%.
The invention effect: dehydration temperaturre is the high-pure anhydrous Lanthanum trichloride of preparation or Cerium II Chloride most critical factor among the present invention, adopt the interior material of temperature programming control body of heater under same temperature, to dewater, control temperature variation ± 1 ℃, because heating member is the external-heat heating, heat-up rate is too fast or soaking time short, it is inhomogeneous to pass to the body of heater internal temperature, can cause near the body of heater temperature of charge is too high hydrolysis very easily takes place, generate LaOCl or CeOCl, and the middle part temperature is on the low side, material dewatering is incomplete, contains water-insoluble in the anhydrous lanthanum chloride that obtains or the Cerium II Chloride and water content is higher, so want strict heat-up rate and the segmentation soaking time set.The ammonium chloride add-on is on the low side, generates LaOCl or CeOCl easily, and the ammonium chloride add-on is higher, and cost is higher, and simultaneously trace impurity can enrichment in product in the ammonium chloride, influences quality product.This technology is applied in every batch in plant-scale temperature programming stove and produces anhydrous lanthanum chloride or Cerium II Chloride 100kg, and the high-pure anhydrous Lanthanum trichloride that obtains or Cerium II Chloride water content are added to the water and dissolve at once less than 0.1%, and the dissolving rear solution is limpid transparent.
Embodiment
Embodiment 1
150kgCeCl
37H
2O crystal and 37.5kg ammonia chloride crystal mix in mixer, mixed material is respectively charged in the porcelain alms bowl, the porcelain alms bowl that will contain material is more evenly put in the temperature programming stove, water also vacuum pump vacuumizes, and when vacuum tightness reaches 0.08Pa, sets heating schedule and begins heating, heating schedule is: room temperature～120 ℃, heat-up rate is 0.83 ℃/minute, and 2 hours heating-up times were 120 ℃ of soaking times 4 hours; 120 ℃～240 ℃, heat-up rate is 2 ℃/minute, and 1 hour heating-up time was 240 ℃ of soaking times 4 hours; 240 ℃～300 ℃, heat-up rate is 0.5 ℃/minute, and 2 hours heating-up times were 300 ℃ of soaking times 2 hours; 300 ℃～360 ℃, heat-up rate is 0.5 ℃/minute, and 2 hours heating-up times were 360 ℃ of soaking times 7 hours, when furnace body temperature drops to 50 ℃ naturally, discharging, vacuum packaging obtains the anhydrous cerium chloride of 98.5kg, detecting water content by analysis is 0.09%, be added to the water and dissolve at once, the dissolving rear solution is limpid transparent, and anhydrous cerium chloride purity is 99.5%.
Embodiment 2
150kg LaCl
37H
2O crystal and 37.5kg ammonia chloride crystal mix in mixer, mixed material is respectively charged in the porcelain alms bowl, the porcelain alms bowl that will contain material is more evenly put in the temperature programming stove, water also vacuum pump vacuumizes, and when vacuum tightness reaches 0.08Pa, sets heating schedule and begins heating, heating schedule is: room temperature～120 ℃, heat-up rate is 0.83 ℃/minute, and 2 hours heating-up times were 120 ℃ of soaking times 4 hours; 120 ℃～240 ℃, heat-up rate is 2 ℃/minute, and 1 hour heating-up time was 240 ℃ of soaking times 4 hours; 240 ℃～300 ℃, heat-up rate is 0.5 ℃/minute, and 2 hours heating-up times were 300 ℃ of soaking times 2 hours; 300 ℃～360 ℃, heat-up rate is 0.5 ℃/minute, 2 hours heating-up times are 360 ℃ of soaking times 7 hours, when furnace body temperature drops to 50 ℃ naturally, discharging, vacuum packaging, it is 0.08% that the anhydrous lanthanum chloride that obtains 98.3kg detects water content by analysis, dissolving at once is added to the water, the dissolving rear solution is limpid transparent, and anhydrous lanthanum chloride purity is 99.6%.
Embodiment 3
150kg CeCl
37H
2O crystal and 37.5kg ammonia chloride crystal mix in mixer, mixed material is respectively charged in the porcelain alms bowl, the porcelain alms bowl that will contain material is more evenly put in the temperature programming stove, water also vacuum pump vacuumizes, and when vacuum tightness reaches 0.08Pa, sets heating schedule and begins heating, heating schedule is: room temperature～120 ℃, heat-up rate is 0.83 ℃/minute, and 2 hours heating-up times were 120 ℃ of soaking times 4 hours; 120 ℃～240 ℃, heat-up rate is 2 ℃/minute, and 1 hour heating-up time was 240 ℃ of soaking times 4 hours; 240 ℃～300 ℃, heat-up rate is 0.5 ℃/minute, and 2 hours heating-up times were 300 ℃ of soaking times 2 hours; 300 ℃～360 ℃, heat-up rate is 0.5 ℃/minute, 2 hours heating-up times are 360 ℃ of soaking times 7.3 hours, when furnace body temperature drops to 50 ℃ naturally, discharging, vacuum packaging, it is 0.07% that the anhydrous cerium chloride that obtains 98.4kg detects water content by analysis, dissolving at once is added to the water, the dissolving rear solution is limpid transparent, and anhydrous cerium chloride purity is 99.7%.
Claims (1)
1. one kind prepares the method for high-pure anhydrous Lanthanum trichloride or Cerium II Chloride by programmed temperature method, it is characterized in that, with directly separating Lanthanum trichloride or the solution of cerium chloride by oxidation heating condensing crystal of preparing from rare earth extraction, obtains particulate state crystal LaCl
37H
2O or CeCl
37H
2O contains lanthanum trioxide or cerium oxide purity greater than 99.99%, LaCl in the rare earth oxide amount
37H
2O or CeCl
37H
2O and ammonium chloride mixed in mixer by weight 4: 1, it is in 1 liter of porcelain alms bowl that mixed material is respectively charged into volume, the porcelain alms bowl that will contain material is more evenly put in the temperature programming stove, vacuumize with water jet pump, when vacuum tightness reaches 0.08Pa, set heating schedule and begin heating, heating schedule is: room temperature～120 ℃, heat-up rate is 0.83 ℃/minute, and 2 hours heating-up times were 120 ℃ of soaking times 4 hours; 120 ℃～240 ℃, heat-up rate is 2 ℃/minute, and 1 hour heating-up time was 240 ℃ of soaking times 4 hours; 240 ℃～300 ℃, heat-up rate is 0.5 ℃/minute, and 2 hours heating-up times were 300 ℃ of soaking times 2 hours; 300 ℃～360 ℃, heat-up rate is 0.5 ℃/minute, and 2 hours heating-up times were 360 ℃ of soaking times 7～7.3 hours, when furnace body temperature drops to 50 ℃ naturally, discharging, vacuum packaging, the anhydrous lanthanum chloride that obtains or Cerium II Chloride, detect water content by analysis less than 0.1%, be added to the water and dissolve at once, the dissolving rear solution is limpid transparent, and product purity is greater than 99%.
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Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103691337A (en) * | 2013-12-12 | 2014-04-02 | 宁夏东方钽业股份有限公司 | Preparation method of anhydrous lanthanum chloride and halogen salt mixture |
| CN104973617A (en) * | 2015-07-01 | 2015-10-14 | 乐山沃耐稀电子材料有限公司 | Preparation method of anhydrous lanthanum chloride |
| CN106915763A (en) * | 2017-05-02 | 2017-07-04 | 乐山沃耐稀电子材料有限公司 | A kind of high-purity anhydrous lanthanum chloride preparation technology |
| CN107601544A (en) * | 2017-09-12 | 2018-01-19 | 中国科学院青海盐湖研究所 | The preparation method of anhydrous neodymium chloride |
| CN107500334A (en) * | 2017-09-12 | 2017-12-22 | 中国科学院青海盐湖研究所 | The preparation method of anhydrous lanthanum chloride |
| CN107827140A (en) * | 2017-09-12 | 2018-03-23 | 中国科学院青海盐湖研究所 | The preparation method of anhydrous rare-earth chlorination |
| CN107500335A (en) * | 2017-09-12 | 2017-12-22 | 中国科学院青海盐湖研究所 | The preparation method of anhydrous cerium chloride |
| CN107827139A (en) * | 2017-09-12 | 2018-03-23 | 中国科学院青海盐湖研究所 | The preparation method of anhydrous praseodymium chloride |
| CN111186853B (en) * | 2018-10-26 | 2021-02-09 | 北京梦晖科技有限公司 | Preparation method of rare earth halide |
| CN110065963A (en) * | 2019-04-26 | 2019-07-30 | 兰州大学 | A kind of preparation method of anhydrous rare-earth chlorination |
| CN112010339B (en) * | 2020-09-04 | 2021-06-18 | 内蒙古蒙稀新材料有限责任公司 | Preparation method of high-purity anhydrous rare earth chloride |
| CN112607761B (en) * | 2020-12-28 | 2022-04-08 | 包头市明芯科技有限公司 | Preparation method of high-purity anhydrous rare earth chloride |
| CN113772714A (en) * | 2021-10-18 | 2021-12-10 | 天津包钢稀土研究院有限责任公司 | Anhydrous samarium chloride and preparation method thereof |
| CN114634198A (en) * | 2022-03-31 | 2022-06-17 | 山东金能环保科技有限公司 | Preparation method of high-purity anhydrous lanthanum chloride |
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