CN1317191C - Process for preparing high purity strontium carbonate - Google Patents
Process for preparing high purity strontium carbonate Download PDFInfo
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- CN1317191C CN1317191C CNB2005100570576A CN200510057057A CN1317191C CN 1317191 C CN1317191 C CN 1317191C CN B2005100570576 A CNB2005100570576 A CN B2005100570576A CN 200510057057 A CN200510057057 A CN 200510057057A CN 1317191 C CN1317191 C CN 1317191C
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Abstract
The present invention relates to a method for preparing strontium carbonate with high purity, which comprises: the mixture composed of celestite, anthracite, a catalytic agent and calcium chloride is used for reduction in a high temperature roasting mode so that strontium sulfide is obtained; after the strontium sulfide is hot leached and filtered, sodium hydroxide is added to the strontium sulfide for alkali out reaction so that crystals of strontium hydroxide octahydrate are generated; then, strontium hydroxide is purified by using recrystallization technology; finally, strontium hydroxide pure solution reacts with led in carbon dioxide under ultrasonic action to generate the powder of the strontium carbonate with high purity; lime milk reacts with the residual liquid of the alkali out reaction of the strontium sulfide to generate sodium hydroxide and strontium sulfide precipitates, wherein the sodium hydroxide is circulated to be used for the alkali out reaction. The present invention has the main advantages of shortest route of the preparation process of SrCO3 with high purity, basically no consumption of chemical raw material, low production cost, simple manufacturing process of impurity removal, no introduction of other impurity ions and easy waste residue treatment.
Description
Technical field
The present invention relates to a kind of preparation method of high-purity strontium carbonate, especially the used in electronic ceramic preparing strontium carbonate.
Background technology
Highly pure strontium carbonate is a kind of important inorganic fine chemical product, is the requisite important source material of electronic industry, and it not only requires the chemical purity height, also requires that the Strontium carbonate powder particle diameter is little, particle size distribution range is narrow and the particle shape sub-circular.Have only a few countries can produce such highly pure strontium carbonate at present in the world as Japan, the U.S. etc.Its manufacture method is many to be raw material with the technical grade Strontium carbonate powder, and preparation technology mainly contains thermal decomposition method and chemical double decomposition.Thermal decomposition method (US3743691, JP59-83934, CN87101234A, CN87104559A, CN1031983A) resolves into strontium oxide with the industrial magnesium strontium roasting, the water-soluble back of the latter forms strontium hydroxide solution, forms the high-purity strontium carbonate product with carbonating reagent reaction (carbonic acid gas, volatile salt, bicarbonate of ammonia etc.) after chemical process is removed foreign ion.And chemical double decomposition also is raw material with the industrial magnesium strontium, with hydrochloric acid, nitric acid, acetic acid, ammonium chloride, ammonium nitrate, ammonium acetate, ammonium formiate, souring agent (CN1035995A such as propionic acid ammonium, CN1394809A, CN1373088A, CN1043482A, CN1057629A, CN1186047) reaction forms soluble strontium salt, again through removing Ba, form the highly pure strontium carbonate product with the carbonating reagent reaction behind the foreign ions such as Ca, such technology is because the Strontium carbonate powder that reaction generates is slightly soluble in above-mentioned reagent, can cause product absorption serious, the partial impurities ion content exceeds standard, the big and wider distribution of particle diameter.
Prepare Strontium carbonate powder with the lazurite direct reaction and mainly contain two class technologies: direct double decomposition of lazurite and lazurite reduction-double decomposition.Direct double decomposition (the CN1394809A of lazurite; " chemical industry mineral and processing " 2002,5:4-7) adopt the reaction of lazurite and soluble carbon hydrochlorate (volatile salt, yellow soda ash etc.) to form thick Strontium carbonate powder, again through acid is molten be soluble strontium salt after, remove foreign ion with a series of chemical processes, last carbonation reaction generates Strontium carbonate powder.The a large amount of chemical industry raw materials of this processes expend (acid, alkali, salt), production cost is high, removal of impurities process complexity, the technology controlling and process strictness very easily causes the Strontium carbonate powder physicochemical property not meet the demands.
The most strontium of China enterprise all produces industrial magnesium strontium with lazurite reduction-double decomposition at present, be that lazurite and carbon are baking mixed, make lazurite be converted into soluble strontium salt strontium sulfide, removal of impurities after direct chemical removal of impurities or chemical conversion again, last carbonic acid changes into Strontium carbonate powder.This method has the following disadvantages: produce a large amount of obnoxious flavour hydrogen sulfide in reaction process, very easily cause environmental pollution, pollution therefore how to control hydrogen sulfide is the key point of this technology of development; Cause the waste of running off in a large number of sulfide in the celestite ore resource.And it is low to use lazurite reduction double decomposition directly to prepare the production cost of high-purity strontium carbonate, but up to the present China to the research that directly prepares high-purity strontium carbonate with this technology, produce still blank.Patent " process for producing strontium carbonate " (CN1042886A) is reacted with hydrochloric acid and strontium sulfide leaching liquid earlier, and then with bicarbonate of ammonia prepared in reaction Strontium carbonate powder, waste gas strontium sulfide CaCN
2Absorb; The also harm of removal of hydrogen sulfide gas from the source of this method, but consume industrial chemicals such as a large amount of hydrochloric acid, bicarbonate of ammonia.And patent " a kind of carbon reduction lazurite is produced the innoxious production technique of Strontium carbonate powder " (CN1562759A) adopts milk of lime and strontium sulfide leaching liquid direct reaction to generate strontium hydroxide and sulfurated lime precipitation, thereby eliminates S from the source
2-Harm; There is a defective in this method---and the strontium hydroxide and the sulfurated lime dissolving of generation are all less even insoluble, and meeting a large amount of strontium hydroxide crystals of generation and sulfurated lime mix after the reaction, can't separate.
Summary of the invention
The objective of the invention is the deficiency at existing Strontium carbonate powder preparation technology, a kind of processing method that directly prepares high-purity strontium carbonate from lazurite is provided, this technical process is short, does not consume industrial chemicals substantially, and cost is low.
Technical scheme provided by the invention is:
(1) be 75～95% lazurite breeze (80～100 order) with Strontium Sulphate content with pulverized anthracite, catalyzer calcium chloride with 100: 60: 0.6 part by weight uniform mixing after, obtain strontium sulfides 1000～1200 ℃ of roastings;
(2) strontium sulfide and deionized water obtained the strontium sulfide hydrothermal solution by 1: 5～8 (weight ratios) in 1～2 hour 75～90 ℃ of leachings, and the stink damp body and function alkali that overflows during leaching is analysed debris and absorbed;
(3) strontium sulfide hydrothermal solution and sodium hydroxide (excessive 5～10%) alkali out reaction formation strontium hydroxide crystal and alkali are analysed debris, and alkali analyses debris and the recovery of milk of lime reaction generation sodium hydroxide is used for alkali out reaction;
(4) solution of strontium hydroxide crystal after 2～3 recrystallizations are purified prepares high-purity strontium carbonate with the carbon dioxide of decomposition of limestone at 75～85 ℃ of scope internal reactions under the ultrasonic stirring effect.
Specifically see Fig. 1, the principal reaction equation that wherein relates to is:
The lazurite reduction reaction:
The strontium sulfide dissolving:
The strontium sulfide partial hydrolysis:
Alkali out reaction:
The decomposition of limestone reaction:
The lime emulsion reaction:
Carbonation reaction:
The off gas treatment reaction:
Or
Sodium hydroxide reclaims reaction:
The present invention has following effect:
(1) in the lazurite reduction process, use catalyzer, can reduce reduction reaction temperature, improve the reduction ratio of lazurite, thereby improve the disposable recovery rate of strontium, and catalyzer calcium chloride at high temperature is gaseous state and overflows, and does not influence the removal of impurities of subsequent technique.
(2) suppress by the pH value of leaching liquid in the control leaching process or reduces overflowing of hydrogen sulfide, and a small amount of hydrogen sulfide that overflows can be with the debris (containing excessive sodium hydroxide) or the milk of lime absorption of alkali out reaction.
(3) adopt the pure solution of recrystallizing technology purified hydrogen strontium oxide, and be that carbonating agent prepares Strontium carbonate powder with the carbonic acid gas, this process does not have other any foreign ion and enters, the purity height of the Strontium carbonate powder of preparation.Can prevent growing up, reuniting of Strontium carbonate powder crystal grain and introduce the ultrasonic stirring system in carbonation, the product particle of preparation is little, narrow diameter distribution and almost spherical.
(4) sulphur among the present invention all exists in solid-state or liquid mode, does not have the generation of hydrogen sulfide obnoxious flavour substantially, and the wastewater treatment closed cycle does not have waste water and gas to discharge except that deslagging, belongs to zero blowdown technology substantially.
(5) the present invention is equipped with a small-sized limestone kiln milk of lime and carbonic acid gas is provided, and the adding of milk of lime recycles sodium hydroxide, consumes little.
(6) operational path of the present invention is short, does not consume other industrial chemicals except that a certain amount of caustic soda, and production cost is low, and the foreign ion of product strontium carbonate, physicochemical property, purity all meet the use standard.
Description of drawings
Fig. 1 is a high-purity strontium carbonate preparation technology schema, and wherein catalyzer is a calcium chloride.
Fig. 2 is the particle size dispersion of high-purity strontium carbonate.
Fig. 3 is the microtexture SEM figure of high-purity strontium carbonate; Wherein a is low power figure, and b is the partial enlarged drawing of figure a.
Fig. 4 is the phase composite analysis chart of high-purity strontium carbonate.
Fig. 5 is the thermal property analytic curve of high-purity strontium carbonate.
Embodiment
Embodiment 1: with content is 93.7% lazurite, hard coal, calcium chloride with 100: 60: 0.6 weight ratio batching, and levigate to 80～120 orders, mixes the back 1000～1200 ℃ of roastings 1～2 hour.The roasting powder leaches while hot, and leaching temperature is 75～90 ℃; The filter residue and drying weighing accounts for 4.5% of roasting grain weight amount, 95.5% roasting powder solubilized is described, the transformation efficiency height of strontium sulfide; Obtain strontium sulfide leaching liquid constant temperature behind the heat filtering and preserve, and analyze Sr
2+Concentration adds NaOH (excessive 5～10%) in proportion, and crystallisation by cooling is separated out strontium hydroxide crystal.Strontium hydroxide crystal directly is dissolved in hot water, feeds carbonic acid gas and reacts, and 75～85 ℃ of temperature of reaction can directly obtain strontium carbonate powder, and purity is 97.48% (seeing Table 1), satisfies the technological standard of industrial magnesium strontium.Filtration residue liquid is used for absorbing the waste gas that leaching process produces, and reclaims sodium hydroxide solution with the milk of lime reaction afterwards, to be used for alkali out reaction.
Embodiment 2: the strontium hydroxide crystal that embodiment 1 is obtained is dissolved in boiling water (100 ℃) and obtains saturated solution, be cooled to 20 ℃ and obtain a recrystallization strontium hydroxide crystal, reaction conditions according to embodiment 1 prepares Strontium carbonate powder, and its purity is 99.24% (seeing Table 1).
Embodiment 3: the crystal that embodiment 2 is obtained carries out secondary or three recrystallizations according to the recrystallizing technology of embodiment 2 once more, and respectively under the effect of ultrasonic system, with carbonic acid gas 75～85 ℃ of reactions, the Strontium carbonate powder purity of acquisition is respectively 99.73%, 99.97% (seeing Table 1).The physicochemical property of the Strontium carbonate powder that secondary recrystallization obtains is seen Fig. 2 (globule size and distribution), Fig. 3 (particle microscopic appearance), Fig. 4 (product facies analysis), Fig. 5 (analysis of product thermal property).From the chemical ingredients of product, analysis of physical and chemical feature as can be known, secondary or secondary recrystallization and the strontium carbonate product that obtains under the ultrasonic wave effect are better than the used in electronic ceramic Strontium carbonate powder standard of Japan, the U.S..
Strontium carbonate powder composition behind the different number of times recrystallizations of table 1
| The recrystallization number of times | SrCO 3/％ | BaO/％ | CaO/％ | Fe 2O 3/％ | Na 2O/％ |
| 0 1 2 3 | 97.48 99.24 99.73 99.97 | 0.51 0.12 0.015 ＜0.01 | 0.32 0.04 0.007 ＜0.01 | 0.007 0.001 ＜0.001 ＜0.001 | - 0.05 ＜0.01 ＜0.01 |
Claims (1)
1. process for preparing high purity strontium carbonate is characterized in that:
(1) with Strontium Sulphate content be 75～95% 80～100 purpose lazurite breezes and pulverized anthracite, catalyzer calcium chloride with 100: 60: 0.6 part by weight uniform mixing after, obtain strontium sulfides 1000～1200 ℃ of roastings;
(2) strontium sulfide and deionized water obtained the strontium sulfide hydrothermal solution by weight 1: 5～1: 8 in 1～2 hour 75～90 ℃ of leachings, and the stink damp body and function alkali that overflows during leaching is analysed debris and absorbed, and its reaction equation is:
(3) strontium sulfide hydrothermal solution and excessive sodium hydrate alkali out reaction formation strontium hydroxide crystal and alkali are analysed debris, and its reaction equation is:
Alkali analyses debris and the milk of lime reaction generates sodium hydroxide, and its reaction equation is:
, the sodium hydroxide of generation reclaims and is used for alkali out reaction;
(4) solution and the carbonic acid gas of strontium hydroxide crystal after 2～3 recrystallizations are purified carries out the prepared in reaction high-purity strontium carbonate under 75～85 ℃, ultrasonic stirring effect, and its reaction equation is:
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100560500C (en) * | 2007-05-24 | 2009-11-18 | 中国科学院青海盐湖研究所 | The preparation method of high-quality strontium carbonate |
| CN102515235A (en) * | 2011-12-31 | 2012-06-27 | 河北辛集化工集团有限责任公司 | Method for preparing strontium hydroxide octahydrate granular crystals |
| CN102765740B (en) * | 2012-06-19 | 2014-03-05 | 南京金焰锶业有限公司 | Preparation method of strontium carbonate with high purity |
| CN103754915B (en) * | 2013-12-13 | 2015-04-29 | 绵阳市远达新材料有限公司 | Preparation method of strontium carbonate |
| CN103864125B (en) * | 2014-01-29 | 2015-08-12 | 南京金焰锶业有限公司 | A kind of automatization preparation facilities of carbonate and method |
| CN108793086A (en) * | 2018-07-23 | 2018-11-13 | 贵州红星发展股份有限公司 | The leaching method and leaching device of alkaline earth sulfide |
| CN109179473B (en) * | 2018-10-24 | 2020-04-28 | 南昌航空大学 | Simple method for preparing coralline strontium carbonate crystal |
| CN112678859A (en) * | 2021-01-28 | 2021-04-20 | 重庆庆龙精细锶盐化工有限公司 | Continuous carbonization reaction system and production process for producing high-purity large-particle-size strontium carbonate |
| CN115432728B (en) * | 2022-10-11 | 2023-04-28 | 南京工程学院 | Method for producing high-purity strontium carbonate by utilizing hydrogen metallurgy technology |
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| US4666688A (en) * | 1986-02-03 | 1987-05-19 | Excel-Mineral Company, Inc. | Method for recovery and conversion of strontium sulfate to strontium carbonate from low and medium grade celestite ores |
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2005
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