CN104291365B - The method of purification rubidium salt - Google Patents
The method of purification rubidium salt Download PDFInfo
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- CN104291365B CN104291365B CN201310304019.0A CN201310304019A CN104291365B CN 104291365 B CN104291365 B CN 104291365B CN 201310304019 A CN201310304019 A CN 201310304019A CN 104291365 B CN104291365 B CN 104291365B
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- hydrogen tartrate
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Abstract
The invention discloses a kind of method of the rubidium salt of purifying, comprise the steps: that (1) joins cleaner in the mixture of water and thick rubidium salt, stir, filter, then add aqueous tartaric acid solution; Stir, Separation of Solid and Liquid, collects hydrogen tartrate rubidium and mother liquor; Described cleaner is selected from oxalic acid, ammonium oxalate, barium hydroxide or brium carbonate; (2) product of step (1) is cooled to below 25 DEG C, Separation of Solid and Liquid, collects respectively hydrogen tartrate rubidium and mother liquor; (3) isolated hydrogen tartrate rubidium is calcined to 2-16 hour at 200-800 DEG C, can obtain the rubidium carbonate after purification. The present invention can decline impurity content one more than the order of magnitude, and the quality of product increases substantially.
Description
Technical field
The present invention relates to a kind of new process of rubidium salt purification.
Background technology
Rubidium is a kind of rare metal, and its esters has obtained at aspects such as electronics, medicine, petrochemical industries moreCarry out more application, in industries such as electronics, require rubidium salt to have higher purity, former technique existsFollowing problem:
Synthetic most of rubidium salt, such as rubidium chloride, rubidium nitrate, rubidium fluoride RbF, rubidium bromide etc., uses conventionallyRubidium carbonate is raw material and corresponding acid reaction, and these rubidium salt solubilities are all very high, the dissolving 15 DEG C timeDegrees of data is roughly as follows:
| Rubidium chloride | Oxalic acid rubidium | Rubidium fluoride RbF | Rubidium bromide | Rubidium carbonate | Rubidium nitrate | |
| Solubility g/100g water | 95 | 190 | 125 | 98 | 450 | 442.8 |
To the soluble impurity in product, such as anion such as sodium, potassium, chlorine, nitrate anions, very difficultTo remove, if with the Methods For Purification being recrystallized, because the solubility of product own is all very large, mother liquorAmount must control seldom can ensure yield, but such refining effect is just very limited, to requiringHigher product, must, through being repeatedly recrystallized, can reach requirement, sodium, potassium and solubility the moonIon will be enriched in mother liquor, cannot process, particularly with the Methods For Purification carbonic acid being recrystallizedRubidium, because alkalescence is very strong, has relatively high expectations to the corrosion resistance of equipment, and is difficult to obtain to separateGo out the solid product of a certain amount of mother liquor, this is the difficult problem always perplexing in industry.
Summary of the invention
The object of the present invention is to provide a kind of method of the rubidium salt of purifying, to overcome, prior art existsAbove-mentioned defect.
Method of the present invention comprises the steps:
(1) cleaner is joined in the mixture of water and thick rubidium salt, stirs 0.2～8 hour, filter,Then adding weight concentration is 10～30% aqueous tartaric acid solution; Stir 0.2～12 hour, solid-liquid dividesFrom, collect hydrogen tartrate rubidium and mother liquor;
Described rubidium salt is selected from rubidium carbonate, rubidium chloride, rubidium fluoride RbF or rubidium nitrate etc.;
In described thick rubidium salt, the weight content of rubidium salt is 80.0-99.9%;
Described tartaric acid selects technical grade, analyze pure or top grade is pure, preferably adopts L-TARTARIC ACID or D-wineStone acid;
Described cleaner is selected from oxalic acid, ammonium oxalate, barium hydroxide or brium carbonate;
The weight ratio of component is:
Thick rubidium salt: water: the aqueous tartaric acid solution that weight concentration is 20-80%
＝1∶0.4～2.0∶1.25～8.0；
Cleaner: thick rubidium salt=1: 100～1000, weight ratio;
(2) be cooled to below 25 DEG C, preferably 5～25 DEG C, by the product Separation of Solid and Liquid of step (1),Collect respectively hydrogen tartrate rubidium and mother liquor;
Preferably, mother liquor is evaporated, cooling rear further recovery hydrogen tartrate rubidium precipitation, or willMother liquor turns back to step (1), for dissolving rubidium carbonate and tartaric acid;
(3) isolated hydrogen tartrate rubidium is calcined to 2-16 hour at 200-800 DEG C, can obtainRubidium carbonate after purification.
Preferably, repeating step (1)～step (3), uses above-mentioned side by the rubidium carbonate obtaining if desiredMethod is further purified, until the quality of product reaches the purity of expection;
Further, also comprise step (4), the rubidium carbonate after the purification that step (3) is obtained and correspondingAnalytically pure acid neutralization, filter, evaporation, dry, can obtain other rubidium salt after purification;
Described acid is analytically pure nitric acid, hydrochloric acid, sulfuric acid or hydrofluoric acid, obtains product and is respectively nitreAcid rubidium, rubidium chloride, rubidium sulfate or rubidium fluoride RbF.
Rubidium carbonate: the acid (nitric acid, hydrochloric acid, sulfuric acid or hydrofluoric acid) that weight concentration is 30-50%
=1:0.35～1.82；
The present invention reacts thick rubidium salt with tartaric acid, obtain the hydrogen tartrate rubidium that solubility is very little, this productSolubility when 25 DEG C of product is only 1.18g/100ml water, and so most rubidiums have just changed into precipitationThing, and the soluble impurities such as sodium, potassium, chlorine are still in solution, after Separation of Solid and Liquid, hydrogen tartrate rubidiumIn the only residual resolvability impurity of minute quantity, changed into rubidium carbonate after this product is added to thermal decomposition,As long as control tartaric quality well, reduce parcel and the attached liquid amount of hydrogen tartrate rubidium precipitation, the effect of purifyingFruit is very remarkable, conventionally impurity content can be declined to one more than the order of magnitude, it is worthy of note thisProcess can repeat, until quality satisfaction. By anti-to the rubidium carbonate obtaining like this and respective acidsShould, just obtain through pervaporation, dry processing all kinds of rubidium product salts that quality increases substantially.
Detailed description of the invention
Embodiment 1
Rubidium carbonate used is technical grade, wherein rubidium carbonate content 99%, major impurity content as sodium, potassium,The content of calcium, magnesium, nitrate anion is 150-2000ppm, and tartaric acid used is technical grade, and content is 99%.
(1) add pure water 200Kg at reactor, add rubidium carbonate 100Kg, stirring and dissolving;
(2) add cleaner oxalic acid 0.4Kg, stirring reaction 2 hours, filters, and collects filtrate;
(3) tartaric acid solution that is 20% by 680Kg weight concentration, adds step (2) under stirringRubidium carbonate solution, after adding, stirs 30 minutes;
(4) be cooled to 25 DEG C, carry out Separation of Solid and Liquid with centrifuge, obtain the wet product of hydrogen tartrate rubidium andMother liquor.
(5) by the calcining of hydrogen tartrate rubidium, temperature is 350 DEG C, and the time is 8 hours, obtains rubidium carbonate and producesProduct 90.5Kg, direct yield 90.5%, impurity content is all lower than 80ppm.
Embodiment 2
Rubidium carbonate used is technical grade, wherein rubidium carbonate content 99%, major impurity content as sodium, potassium,The content of calcium, magnesium, chlorine, nitrate anion is 150-2000ppm, and tartaric acid used is technical grade, and content is99%。
(1) the mother liquor 200Kg that adds embodiment 1 step (4) to produce at reactor, adds rubidium carbonate100Kg, stirring and dissolving.
(2) add cleaner oxalic acid 0.35Kg, stirring reaction 4 hours, filters, and collects filtrate;
(3) by 680Kg weight concentration be the rubidium carbonate solution that 20% tartaric acid solution adds step (2),After adding, stir 30 minutes;
(4) be cooled to 20 DEG C, carry out liquid-solid separation with centrifuge, obtain the wet product of hydrogen tartrate rubidium andMother liquor;
(5) by the calcining of hydrogen tartrate rubidium, temperature is 350 DEG C, and the time is 8 hours, obtains rubidium carbonate and producesProduct 101.5Kg, direct yield 101.5%, exceeding 100% yield is to cause because this chilling temperature is lower, impurity content is all lower than 100ppm.
The mother liquor producing can continue according to said method to recycle, or directly evaporation and concentration reclaims.
Embodiment 3
Rubidium carbonate used is 99.5% rank, wherein rubidium carbonate content 99.5%, major impurity content as sodium,The content of potassium, calcium, magnesium, chlorine, nitrate anion is 20-500ppm, and tartaric acid used is pure for analyzing, contentBe 99%.
After the process of pressing embodiment 1 is processed, direct yield is about 90.3%, and impurity content is all lower than 50ppm.
Embodiment 4
Rubidium carbonate used is technical grade, wherein rubidium carbonate content 98%, major impurity content as sodium, potassium, calcium,The content of magnesium, chlorine, nitrate anion is 350-2000ppm, and tartaric acid used is technical grade, and content is 99%.
500L plastics add pure water 100Kg, add rubidium carbonate 100Kg, stirring and dissolving, and removal of impurities is filtered.
All the other are 450 DEG C at calcining by hydrogen tartrate rubidium in temperature according to the method processing of embodiment 1,Time is 6 hours, obtains product 90.5Kg, direct yield 92.3%, and impurity content is all lower than 100ppm.
Embodiment 5
(1) reactor adds pure water 100Kg, adds technical grade rubidium nitrate 75Kg, and Na, K, Cl etc. are assortedMatter content is at 500-1500ppm, stirring and dissolving;
(2) add cleaner barium hydroxide 0.2Kg, stirring reaction 2 hours, filters, and collects filtrate;
(3) be 20% tartaric acid solution by 400Kg weight concentration, add the rubidium nitrate of step (2) moltenLiquid, adds rear stirring 30 minutes;
(4) be cooled to 20 DEG C, carry out liquid-solid separation with centrifuge, obtain the wet product of hydrogen tartrate rubidium andMother liquor, further recovery hydrogen tartrate rubidium can be reused or evaporate to mother liquor.
(5) hydrogen tartrate rubidium is calcined in high-temperature blast baking oven, temperature is 350 DEG C, and the time is 8 littleTime, obtain rubidium carbonate 52.6Kg, the yield of rubidium is about 90.5%, the impurity contents such as Na, K, Cl all lower than100ppm。
(6) rubidium carbonate of acquisition is joined in the pure nitric acid of analysis of 57Kg50%, filter, evaporation,Be dried, at least reached the rubidium nitrate of 99.5% above standard;
Embodiment 6
Rubidium nitrate in embodiment 5 is changed to rubidium chloride, and the amount of rubidium chloride is 61.5Kg, and all the other are according to realityExecute the method for example 5, wherein, step (6) is analytically pure hydrochloric acid, is at least reached more than 99.5%The rubidium chloride of standard, yield 90.5% left and right.
Embodiment 7
Rubidium nitrate in embodiment 5 is changed to rubidium fluoride RbF, and the amount of rubidium fluoride RbF is 53Kg, and all the other are real according to pressingExecute the method for example 5, wherein, step (6) is analytically pure hydrofluoric acid, obtain at least reach 99.5% withThe rubidium fluoride RbF of upper standard.
Claims (4)
1. the method for purification rubidium salt, is characterized in that, comprises the steps:
(1) cleaner is joined in the mixture of water and thick rubidium salt, stir 0.2～8 hour, filter, then addEnter weight concentration and be 10～30% aqueous tartaric acid solution; Stir 0.2～12 hour, Separation of Solid and Liquid, collects wineStone acid hydrogen rubidium and mother liquor; Described cleaner is selected from oxalic acid, ammonium oxalate, barium hydroxide or brium carbonate;
(2) product of step (1) is cooled to below 25 DEG C, Separation of Solid and Liquid, collect respectively hydrogen tartrate rubidium andMother liquor;
(3) isolated hydrogen tartrate rubidium is calcined to 2-16 hour at 200-800 DEG C, can obtain after purificationRubidium carbonate;
Described rubidium salt is selected from rubidium carbonate, rubidium chloride, rubidium fluoride RbF or rubidium nitrate, in described thick rubidium salt, and the weight of rubidium saltContent is 99.0-99.9%;
The weight ratio of each component is:
Thick rubidium salt: water: aqueous tartaric acid solution=1 that weight concentration is 20-80%: 0.4～2.0: 1.25～8.0;
Cleaner: thick rubidium salt=1: 100～1000, weight ratio.
2. method according to claim 1, is characterized in that, the mother liquor that step (2) is obtained carries outEvaporation, cooling rear further recovery hydrogen tartrate rubidium precipitation, or mother liquor is turned back to step (1), for moltenSeparate rubidium carbonate and tartaric acid.
3. method according to claim 1, is characterized in that, repeating step (1)～step (3),The rubidium carbonate obtaining is further purified with said method, until the quality of product reaches the purity of expection.
4. method according to claim 3, is characterized in that, also comprises step (4), by step (3)Rubidium carbonate after the purification obtaining and corresponding analytically pure acid neutralization, filtration, evaporation, dry, can obtainOther rubidium salt after purification;
Described acid is analytically pure nitric acid, hydrochloric acid, sulfuric acid or hydrofluoric acid, obtains product and is respectively rubidium nitrate, chlorinationRubidium, rubidium sulfate or rubidium fluoride RbF, rubidium carbonate: acid=1:0.35～1.82 that weight concentration is 30-50%.
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| CN102030346A (en) * | 2009-09-25 | 2011-04-27 | 上海中锂实业有限公司 | Preparation method for lithium carbonate |
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| CN102030346A (en) * | 2009-09-25 | 2011-04-27 | 上海中锂实业有限公司 | Preparation method for lithium carbonate |
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| Title |
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| "提铷技术研究进展";曹冬梅等;《盐业与化工》;20110131;第40卷(第1期);44-47 * |
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Address after: 201417 Shanghai city Fengxian District Zhelin town science Road No. 1158 Applicant after: Shanghai China Lithium Industrial Co., Ltd. Address before: Fengxian District Zhelin Town East Zhongxing Road 201424 Shanghai City No. 8 Applicant before: Shanghai China Lithium Industrial Co., Ltd. |
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