JP2011121853A - Method for producing strontium chloride hexahydrate - Google Patents

Method for producing strontium chloride hexahydrate Download PDF

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JP2011121853A
JP2011121853A JP2010164542A JP2010164542A JP2011121853A JP 2011121853 A JP2011121853 A JP 2011121853A JP 2010164542 A JP2010164542 A JP 2010164542A JP 2010164542 A JP2010164542 A JP 2010164542A JP 2011121853 A JP2011121853 A JP 2011121853A
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chloride hexahydrate
strontium chloride
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JP5241778B2 (en
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Zhiguang Jiang
姜志光
Dong Hua
華東
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Chongqing Kechang Science & Technology Co Ltd
Guizhou Redstar Developing Co Ltd
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    • 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
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/20—Halides
    • C01F11/24—Chlorides
    • C01F11/28—Chlorides by chlorination of alkaline-earth metal compounds
    • 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
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • 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
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/20—Halides
    • C01F11/24—Chlorides
    • C01F11/30—Concentrating; Dehydrating; Preventing the adsorption of moisture or caking
    • 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
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/20—Halides
    • C01F11/24—Chlorides
    • C01F11/32—Purification

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Abstract

<P>PROBLEM TO BE SOLVED: To solve an agglomerate problem of strontium chloride hexahydrate material. <P>SOLUTION: A method for producing strontium chloride hexahydrate comprises the step of obtaining a solution by preparing a slurry by adding water to SrCO<SB>3</SB>, adding hydrochloric acid to the slurry and solving; the step of oxidizing impurities such as iron by adding a hydrogen peroxide to the solution; the step of adjusting the solution to be pH=8-9 in Sr(OH)<SB>2</SB>8H<SB>2</SB>O after heating until the obtained solution boils; the step of cooling and crystallizing a clear solution obtained by filtering the obtained solution under pressure to separate by evaporating the obtained clear solution to concentrate the Baume degree to 48-50; and the step of obtaining SrCl<SB>2</SB>6H<SB>2</SB>O by drying a solid crystal obtained by filtering the obtained crystal under pressure to separate, controlling a free moisture content of the crystal (wt.%) to ≤2%, then performing drying operation to the crystal by using heated air, and controlling a free moisture content of the crystal (wt.%) to ≤0.2%. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

本発明は塩化ストロンチウム六水和物の製造方法に関する。   The present invention relates to a method for producing strontium chloride hexahydrate.

塩化ストロンチウム六水和物材料は、液晶ガラス基板に用いられ、ガラス基板の主結晶相材料として、需要が絶えず増えている。しかし、従来プロセスで製造した塩化ストロンチウム六水和物は、遊離水分量が不安定であるので、集塊や凝固が発生しやすく、実用に大きな問題がある。本発明者らは、集塊のメカニズムを鋭意検討した結果、塩化ストロンチウム六水和物の集塊の原因が、塩化ストロンチウム六水和物が一定量の遊離水を含有し、かつ、塩化ストロンチウム六水和物の溶解度が非常に大きいため、結晶同士接触する境界に溶解・成長過程が起こり、成長過程中、遊離水を排出し、より大きい範囲の溶解・成長を引き起こし、広範囲の集塊を形成してしまうからである、との知見を得るに至った。   The strontium chloride hexahydrate material is used for a liquid crystal glass substrate, and the demand is constantly increasing as a main crystal phase material of the glass substrate. However, since strontium chloride hexahydrate produced by a conventional process has an unstable amount of free water, agglomeration and coagulation are likely to occur, and there is a great problem in practical use. As a result of intensive investigation of the agglomeration mechanism, the present inventors have found that the cause of agglomeration of strontium chloride hexahydrate is that strontium chloride hexahydrate contains a certain amount of free water and strontium chloride hexahydrate. The solubility of hydrates is so high that dissolution / growth processes occur at the boundaries where crystals come into contact with each other. During the growth process, free water is discharged, causing a larger range of dissolution / growth, and forming a wider agglomeration. As a result, they have come to obtain knowledge that this is the case.

本発明は、塩化ストロンチウム六水和物材料の集塊問題を解決することを主な目的とする。   The main object of the present invention is to solve the agglomeration problem of strontium chloride hexahydrate material.

本発明者らは、集塊メカニズムの研究に基づき、従来の製造プロセスを改良し、結晶の表面を二回乾燥する過度乾燥固化法により、塩化ストロンチウム六水和物結晶の表面の水分を乾燥させ、結晶分子１つあたりの表面の結晶水を６つ未満の状態にし、溶解・成長による集塊問題を解決した。   Based on the study of the agglomeration mechanism, the present inventors have improved the conventional manufacturing process and dried the surface moisture of the strontium chloride hexahydrate crystal by an over-drying solidification method in which the crystal surface is dried twice. The crystal water on the surface per crystal molecule was reduced to less than 6 to solve the agglomeration problem due to dissolution / growth.

本発明は、塩化ストロンチウム六水和物の製造方法であって、
SrCO3 に水を加えてスラリを調製し、そのスラリに塩酸を加え、溶解し、溶液を得るステップ１；
ステップ１で得た溶液に過酸化水素加えて鉄などの不純物を酸化するステップ２；
ステップ２で得た溶液を沸騰するまで昇温した後、Sr(OH)2 ・８H2 Oにてその溶液をｐＨ＝８−９に調節するステップ３；
ステップ３で得た溶液を加圧濾過し分離して得た清澄液を蒸発させボーメ度４８−５０まで濃縮し（一般に、該蒸発操作は蒸発缶内で行う）、こうして得た清澄液を冷却結晶する（一般に、該結晶操作は冷却結晶缶内で行う）ステップ４、また、ステップ４の二回の加圧濾過は、いずれも加圧濾過機にて行うことができる；
ステップ４で得た結晶を加圧濾過し分離して得た固体結晶を乾燥し、結晶の遊離水分含量（重量％）を２％以下にコントロールした後、結晶に対して熱風での乾燥操作（該乾燥操作を気流乾燥装置で行う）を行い、結晶の遊離水分含量（重量％）を０．２％以下にコントロールし、冷却し、SrCl2・６H2Oを得るステップ５；を含む方法が提供される。 The present invention relates to a method for producing strontium chloride hexahydrate,
Preparing a slurry by adding water to SrCO 3 and adding hydrochloric acid to the slurry to dissolve it to obtain a solution; step 1;
Adding hydrogen peroxide to the solution obtained in step 1 to oxidize impurities such as iron; step 2;
After the temperature of the solution obtained in Step 2 is raised to boiling, the solution is adjusted to pH = 8-9 with Sr (OH) 2 .8H 2 O Step 3;
The solution obtained in step 3 under pressure spent concentrating the separated-obtained clear liquid to Baume 48-50 evaporated (generally, evaporation operation is carried out in the evaporator), so obtained clear solution cooled Crystallize (generally, the crystallization operation is performed in a cooled crystal can), and the two pressure filtrations in step 4 can both be performed in a pressure filter;
The crystals obtained in Step 4 are filtered under pressure and separated, and the solid crystals obtained are dried. After controlling the free water content (wt%) of the crystals to 2% or less, the crystals are dried with hot air ( Performing the drying operation with an air-flow dryer), controlling the free water content (% by weight) of the crystals to 0.2% or less, and cooling to obtain SrCl 2 .6H 2 O. Provided.

好ましくは、前記ステップ５において、さらに、調製したSrCO3 溶液に加圧濾過し分離して得た母液を戻すステップを含み、そのときのステップ１がSrCO3 に該母液を加えてスラリを調製するステップになる。 Preferably, in step 5, further comprising the step of returning the prepared SrCO 3 solution under pressure spent separated mother liquor obtained, step 1 at that time to prepare a slurry by adding mother liquor to SrCO 3 Become a step.

好ましくは、前記ステップ５において、一回目の乾燥を振動流動床にて行う。   Preferably, in the step 5, the first drying is performed in a vibrating fluidized bed.

好ましくは、前記ステップ５において、熱風の乾燥操作の温度が１８０−２３０℃である。   Preferably, in step 5, the temperature of the hot air drying operation is 180-230 ° C.

本発明における主な化学反応は以下の通りです。
（化１）
SrCO3+2HCl→SrCl2+H2O+CO2↑
（化２）
MgCl2+Sr(OH)2+H2O→Mg(OH)2↓+SrCl2
（化３）
Fe2++H2O2→Fe3+→Fe(OH)3↓ The main chemical reactions in the present invention are as follows.
(Chemical formula 1)
SrCO 3 + 2HCl → SrCl 2 + H 2 O + CO 2 ↑
(Chemical formula 2)
MgCl 2 + Sr (OH) 2 + H 2 O → Mg (OH) 2 ↓ + SrCl 2
(Chemical formula 3)
Fe 2+ + H 2 O 2 → Fe 3+ → Fe (OH) 3 ↓

本発明の方法で製造した塩化ストロンチウム六水和物製品は、外観がルーズな結晶（ＬＯＯＳＥＮ ＣＲＹＳＴＡＬＬＩＮＥ）であり、遊離水含量が０．２％未満で安定であり、集塊問題を大幅に改善した。また、本発明の方法で製造した塩化ストロンチウム六水和物製品は、不純物が少なく、液晶ガラス基板に用いる塩化ストロンチウム六水和物材料の集塊問題を解決し、下流産業の輸送、原料配合、混合の工程の要求に満足した。   The strontium chloride hexahydrate product produced by the method of the present invention is a crystal having a loose appearance (LOOSEN CRYSTALLINE), stable at a free water content of less than 0.2%, and greatly improved the agglomeration problem. . In addition, the strontium chloride hexahydrate product manufactured by the method of the present invention has few impurities, solves the agglomeration problem of strontium chloride hexahydrate material used for the liquid crystal glass substrate, transport of downstream industries, blending raw materials, We were satisfied with the requirements of the mixing process.

本発明の主なプロセスのフローチャートである。3 is a flowchart of the main process of the present invention.

呼び容積１０ｍ3 のエナメル反応釜に母液２ｍ3を加え、工業用炭酸ストロンチウム３トンを投入し、攪拌しながら工業用塩酸を加入し、溶解する。その後、濃度２７．５％工業用過酸化水素２５Ｌを加え、酸化反応を行う。酸化した溶液を昇温し沸騰させ、この溶液にSr（OH）2 ・８H2Oを用い、ｐＨを８に調節する。 Add 2m 3 of mother liquor to an enamel reactor with a nominal volume of 10m 3 , add 3 tons of industrial strontium carbonate, add industrial hydrochloric acid with stirring and dissolve. Thereafter, 25 L of industrial hydrogen peroxide having a concentration of 27.5% is added to carry out an oxidation reaction. The oxidized solution is heated to boiling and the pH is adjusted to 8 using Sr (OH) 2 .8H 2 O for this solution.

調節した溶液を加圧濾過機でろ過し、得た清澄液を蒸発缶に輸送し、ボーメ度４８まで濃縮した後、こうして得た清澄液を冷却結晶缶に輸送し、冷却結晶する。   The adjusted solution is filtered with a pressure filter, and the resulting clear solution is transported to an evaporator and concentrated to a Baume degree of 48. The clear solution thus obtained is transported to a cooling crystal can and cooled and crystallized.

こうして得た結晶を吸引濾過し分離し、得た固体結晶を振動流動床に輸送し、一回目の乾燥を行い、測定された結晶の遊離水分は１．９％である。その後、さらに、その結晶を気流乾燥装置に輸送し、二回目の乾燥を行い、そのときの熱風温度が１８０℃であり、測定された結晶の遊離水分は０．１６％である。乾燥を停止し、結晶が冷却された後、SrCl2 ・６H2 O試料１# を得る。 The crystals thus obtained are separated by suction filtration, and the obtained solid crystals are transported to a vibrating fluidized bed and dried for the first time. The measured free moisture of the crystals is 1.9%. Thereafter, the crystals are further transported to an airflow drying device and dried for the second time. The hot air temperature at that time is 180 ° C., and the measured free moisture of the crystals is 0.16%. After the drying is stopped and the crystals are cooled, SrCl 2 .6H 2 O sample 1 # is obtained.

呼び容積１０ｍ3のエナメル反応釜に母液２ｍ3を加え、工業用炭酸ストロンチウム３トンを投入し、攪拌しながら工業用塩酸を加入し、溶解する。そして、得た溶液に濃度２７．５％工業用過酸化水素２５Ｌを加え、酸化反応を行う。酸化した溶液を昇温し沸騰させ、この溶液にSr（OH）2・８H2Oを用い、ｐＨを９に調節する。 Add 2m 3 of mother liquor to an enamel reactor with a nominal volume of 10m 3 , add 3 tons of industrial strontium carbonate, add industrial hydrochloric acid with stirring and dissolve. Then, 25 L of industrial hydrogen peroxide having a concentration of 27.5% is added to the obtained solution to carry out an oxidation reaction. The oxidized solution is heated to boiling and the pH is adjusted to 9 using Sr (OH) 2 .8H 2 O for this solution.

調節した溶液を加圧濾過機でろ過し、得た清澄液を蒸発缶に輸送し、ボーメ度５０まで濃縮した後、こうして得た清澄液を冷却結晶缶に輸送し、冷却結晶する。   The adjusted solution is filtered with a pressure filter, and the resulting clear solution is transported to an evaporator and concentrated to a Baume degree of 50, and then the clear solution thus obtained is transported to a cooling crystal can and cooled and crystallized.

こうして得た結晶を吸引濾過し分離し、得た固体結晶を振動流動床に輸送し、一回目の乾燥を行い、測定された結晶の遊離水分が１．７％である。その後、さらに、その結晶を気流乾燥装置に輸送し、二回目の乾燥を行い、そのときの熱風温度が２３０
℃であり、測定された結晶の遊離水分が０．１０％である。乾燥を停止し、結晶が冷却された後、SrCl2・６H2O試料２#を得る。
以上の実施例で得た製品のパラメーターを以下の表１に示す。 The crystals thus obtained are separated by suction filtration, and the obtained solid crystals are transported to a vibrating fluidized bed and dried for the first time. The measured free moisture of the crystals is 1.7%. Thereafter, the crystals are further transported to an air flow drying device and dried for the second time, and the hot air temperature at that time is 230.
The measured free water of the crystals is 0.10%. After drying is stopped and the crystals are cooled, SrCl 2 .6H 2 O sample 2 # is obtained.
The parameters of the products obtained in the above examples are shown in Table 1 below.

Figure 2011121853
Figure 2011121853

Claims (4)

SrCO3に水を加えてスラリを調製し、そのスラリに塩酸を加え、溶解し、溶液を得るステップ１；
ステップ１で得た溶液に過酸化水素加えて鉄などの不純物を酸化するステップ２；
ステップ２で得た溶液を沸騰するまで昇温した後、Sr(OH)2・８H2Oにてその溶液をｐＨ＝８−９に調節するステップ３；
ステップ３で得た溶液を加圧濾過し分離して得た清澄液を蒸発させボーメ度４８−５０まで濃縮し、こうして得た清澄液を冷却結晶するステップ４；
ステップ４で得た結晶を加圧濾過し分離して得た固体結晶を乾燥し、結晶の遊離水分含量（重量％）を２％以下にコントロールし、その後、さらに、結晶に対して熱風で乾燥操作を行い、結晶の遊離水分含量（重量％）を０．２％以下にコントロールし、冷却し、SrCl2・６H2Oを得るステップ５；
を含むことを特徴とする塩化ストロンチウム六水和物の製造方法。 Preparing a slurry by adding water to SrCO 3 and adding hydrochloric acid to the slurry to dissolve it to obtain a solution; step 1;
Adding hydrogen peroxide to the solution obtained in step 1 to oxidize impurities such as iron; step 2;
After the temperature of the solution obtained in Step 2 is raised to boiling, the solution is adjusted to pH = 8-9 with Sr (OH) 2 .8H 2 O Step 3;
The solution obtained in Step 3 is filtered under pressure and separated, and the resulting clear solution is evaporated and concentrated to a Baume degree of 48-50, and the clear solution thus obtained is cooled and crystallized; Step 4;
The crystals obtained in Step 4 are filtered under pressure and separated, and the solid crystals obtained are dried. The free water content (% by weight) of the crystals is controlled to 2% or less. Step 5 is performed to control the free water content (wt%) of the crystals to 0.2% or less, and cooling to obtain SrCl 2 · 6H 2 O;
A process for producing strontium chloride hexahydrate, comprising: 前記ステップ５において、加圧濾過し分離して得た母液を調製したSrCO3溶液に戻すステップを含み、そのときのステップ１がSrCO3に該母液を加えてスラリを調製するステップになることを特徴とする請求項１に記載の塩化ストロンチウム六水和物の製造方法。 In the step 5, including the step of returning the SrCO 3 solution prepared mother liquor obtained by under pressure spent separation, that Step 1 at that time is the step of preparing a slurry by adding mother liquor to SrCO 3 The method for producing strontium chloride hexahydrate according to claim 1. 前記ステップ５において、一回目の乾燥を振動流動床にて行うことを特徴とする請求項１に記載の塩化ストロンチウム六水和物の製造方法。 2. The method for producing strontium chloride hexahydrate according to claim 1, wherein in step 5, the first drying is performed in a vibrating fluidized bed. 前記ステップ５において、熱風での乾燥操作の温度が１８０−２３０℃であることを特徴とする請求項１に記載の塩化ストロンチウム六水和物の製造方法。 2. The method for producing strontium chloride hexahydrate according to claim 1, wherein in step 5, the temperature of the drying operation with hot air is 180 to 230 ° C. 3.
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