JPH06127944A - Production of aqueous zirconium chloride solution - Google Patents
Production of aqueous zirconium chloride solutionInfo
- Publication number
- JPH06127944A JPH06127944A JP27836692A JP27836692A JPH06127944A JP H06127944 A JPH06127944 A JP H06127944A JP 27836692 A JP27836692 A JP 27836692A JP 27836692 A JP27836692 A JP 27836692A JP H06127944 A JPH06127944 A JP H06127944A
- Authority
- JP
- Japan
- Prior art keywords
- hydrochloric acid
- slurry
- water
- added
- silica
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/20—Faujasite type, e.g. type X or Y
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ジルコンサンドをアル
カリで処理し、水で浸出処理して得た水浸出ケークに、
塩酸を添加してジルコニウム分を抽出すると同時にシリ
カ分は不溶解化させ、ろ過することによってジルコニウ
ム塩化物水溶液を製造する方法に関する。BACKGROUND OF THE INVENTION The present invention relates to a water-leached cake obtained by treating zircon sand with an alkali and leaching with water.
The present invention relates to a method for producing an aqueous zirconium chloride solution by adding hydrochloric acid to extract a zirconium component, and at the same time insolubilizing a silica component and filtering.
【０００２】ジルコニウム塩化物水溶液からオキシ塩化
ジルコニウム、水酸化ジルコニウム、塩基性硫酸ジルコ
ニウム等の各種ジルコニウム化合物が製造される。この
うち、オキシ塩化ジルコニウム（以下、ＺＯＣという）
は、ジルコニア質セラミックスの出発原料として使われ
る重要な化合物である。Various zirconium compounds such as zirconium oxychloride, zirconium hydroxide and basic zirconium sulfate are produced from a zirconium chloride aqueous solution. Of these, zirconium oxychloride (hereinafter referred to as ZOC)
Is an important compound used as a starting material for zirconia-based ceramics.
【０００３】[0003]
【従来の技術】ジルコニウム塩化物水溶液は、一般にジ
ルコンサンドをアルカリ剤と共に加熱溶融するかまたは
水熱処理し、えられた反応混合物を水で浸出処理して主
としてケイ酸アルカリを溶出させ、水酸化ジルコニウム
を主成分とする水浸出ケークを得、これを塩酸で抽出処
理してジルコニウム塩化物の水溶液とするとともに、残
存するシリカ分を不溶解化させ、ろ過することによって
製造される。この方法の改良として、上記の水浸出ケー
クを６０〜１００℃の温度範囲で濃塩酸に溶解した後、
０．２〜１．０ｇ／ｌのゼラチンを添加し、ゲル状シリ
カ分を凝集沈澱させた後、ろ別してシリカ分を分離する
方法が知られている。A zirconium chloride aqueous solution is generally prepared by heating and melting zircon sand together with an alkali agent or hydrothermally treating it, and leaching the obtained reaction mixture with water to elute mainly alkali silicate, and zirconium hydroxide. It is produced by obtaining a water-leached cake containing as a main component, extracting this with hydrochloric acid to form an aqueous solution of zirconium chloride, insolubilizing the remaining silica content, and filtering. As an improvement of this method, after dissolving the above water-leached cake in concentrated hydrochloric acid in the temperature range of 60 to 100 ° C.,
A method is known in which 0.2 to 1.0 g / l of gelatin is added, the gel-like silica content is coagulated and precipitated, and then the silica content is separated by filtration.
【０００４】[0004]
【発明が解決しようとする課題】しかし、この工業的製
法における最大の問題点は、酸抽出により不溶解化する
シリカ（ＳｉＯ2・ｎＨ2Ｏ）のろ過性が悪いこと及びろ
過後の塩化物水溶液に溶解シリカ分が多量存在すること
である。不溶解シリカは、かさ高いゲル状態で析出する
ために、ろ過が極めて困難であり、かつ洗浄もままなら
ない。よって、ろ過装置は大型化するし、シリカケーク
中には目的物であるジルコニウム分が相当量包含されそ
の損失を避けることができない。However, the biggest problem in this industrial process is that silica (SiO 2 .nH 2 O), which is insolubilized by acid extraction, has poor filterability and chloride after filtration. That is, a large amount of dissolved silica is present in the aqueous solution. Insoluble silica is extremely difficult to filter because it precipitates in a bulky gel state, and cannot be washed. Therefore, the size of the filter becomes large, and a considerable amount of zirconium, which is the target substance, is contained in the silica cake, and its loss cannot be avoided.
【０００５】上記の高温の濃塩酸に溶解した後、ゼラチ
ンを添加する方法でも、ゼラチンの添加によって除去し
うるシリカは粒子化したものだけであって溶解状態にあ
るシリカを除去することはできない。この溶解性シリカ
の重合・ゲル化には数日間を必要とする。溶解性シリカ
を含むジルコニウム塩化物水溶液を原料としてジルコニ
ウム化合物を製造すると、シリカ分が不純物として製品
に混入する。Even with the method of adding gelatin after dissolving in concentrated hydrochloric acid at a high temperature as described above, the silica which can be removed by adding gelatin is only the granulated silica, and the silica in the dissolved state cannot be removed. It takes several days to polymerize and gel the soluble silica. When a zirconium compound is produced using a zirconium chloride aqueous solution containing soluble silica as a raw material, the silica content is mixed as an impurity in the product.
【０００６】本発明は、以上のような問題点に鑑みてな
されたものであり、その目的は、効果的かつ効率的に水
浸出ケークから、溶解シリカ量が少なく、かつ、ろ過性
のよい析出シリカ粒子を含む塩酸抽出液を生成させ、そ
れによってＺＯＣの製造に好適なシリカ分の少ないジル
コニウム塩化物水溶液を製造することができる方法を提
供することにある。The present invention has been made in view of the above problems, and an object thereof is to effectively and efficiently precipitate a water-leached cake with a small amount of dissolved silica and good filterability. It is an object of the present invention to provide a method capable of producing a hydrochloric acid extract containing silica particles and thereby producing an aqueous zirconium chloride solution having a low silica content, which is suitable for producing ZOC.
【０００７】[0007]
【課題を解決するための手段】本発明は、ジルコンサン
ドのアルカリ処理物を水で浸出処理し、ろ過して得た水
浸出ケークを塩酸によって抽出してジルコニウム塩化物
水溶液を製造する方法において、該ケークに水を加えス
ラリーとし、該スラリーを撹拌しつつこれに塩酸を、得
られる懸濁液の液相におけるジルコニウム塩化物のＺｒ
Ｏ2換算濃度が９〜１６ｗｔ％となり、かつ、遊離ＨＣ
ｌ濃度が１〜７ｗｔ％となるように加え、次いでろ過す
ることからなるジルコニウム塩化物水溶液の製造方法で
ある。The present invention provides a method for producing an aqueous zirconium chloride solution by leaching an alkali-treated zircon sand with water and extracting a water-leached cake obtained by filtration with hydrochloric acid. Water is added to the cake to make a slurry, and hydrochloric acid is added to the slurry while stirring the slurry, and Zr of zirconium chloride in the liquid phase of the resulting suspension is added.
O 2 conversion concentration becomes 9 to 16 wt% and free HC
This is a method for producing an aqueous zirconium chloride solution, which comprises adding l so as to have a concentration of 1 to 7 wt% and then filtering.
【０００８】以下、本発明を詳細に説明する。The present invention will be described in detail below.
【０００９】ジルコンサンドのアルカリによる処理は、
一般にジルコンサンドと苛性ソーダ及び／又は炭酸ソー
ダとの混合物の高温加熱処理（アルカリ融解）または水
熱処理によって行われ、生成物としては、反応条件によ
り変動するが、概ねジルコン酸ソーダ，ケイジルコン酸
ソーダ，ケイ酸ソーダおよび未反応のジルコンサンドか
らなる。この処理における反応は下記の式で表されるも
のと推定される。The treatment of zircon sand with alkali is
Generally, a mixture of zircon sand and caustic soda and / or sodium carbonate is subjected to high-temperature heat treatment (alkali melting) or hydrothermal treatment, and the product varies depending on the reaction conditions. Consists of sodium silicate and unreacted zircon sand. The reaction in this treatment is presumed to be represented by the following formula.
【００１０】ＺｒＳｉＯ4＋６ＮａＯＨ→Ｎａ2ＺｒＯ3
＋Ｎａ4ＳｉＯ4＋３Ｈ2Ｏ↑ ＺｒＳｉＯ4＋２ＮａＯＨ→Ｎａ2ＺｒＳｉＯ5＋Ｈ2Ｏ↑ ＺｒＳｉＯ4＋２Ｎａ2ＣＯ3→Ｎａ2ＺｒＯ3＋Ｎａ2Ｓｉ
Ｏ3＋２ＣＯ2↑ ＺｒＳｉＯ4＋Ｎａ2ＣＯ3→Ｎａ2ＺｒＳｉＯ5＋ＣＯ2↑ 本発明は、これらアルカリ融解や水熱処理をどのような
条件で行ったものにも適用することができる。ZrSiO 4 +6 NaOH → Na 2 ZrO 3
+ Na 4 SiO 4 + 3H 2 O ↑ ZrSiO 4 + 2NaOH → Na 2 ZrSiO 5 + H 2 O ↑ ZrSiO 4 + 2Na 2 CO 3 → Na 2 ZrO 3 + Na 2 Si
O 3 + 2CO 2 ↑ ZrSiO 4 + Na 2 CO 3 → Na 2 ZrSiO 5 + CO 2 ↑ The present invention can be applied to any of these conditions in which alkali melting or hydrothermal treatment is performed.
【００１１】このようにしてえられたアルカリ処理物を
水で浸出すると、ジルコン酸ソーダが加水分解を受けて
水酸化ジルコニウムと苛性ソーダが生成する。次いでろ
過によってケイ酸ソーダおよび過剰のアルカリを除去し
て得られる固形物が水浸出ケークである。水浸出ケーク
は、主に、水酸化ジルコニウム，ジルコン酸ソーダ，ケ
イジルコン酸ソーダおよび未反応のジルコンサンド（Ｚ
ｒ砂）からなる。水浸出ケークの組成分析の一例を次に
示す。これは、アルカリ剤として苛性ソーダを用い、６
５０℃で加熱溶融して得た反応溶融物を、水浸出の後に
ろ別・洗浄して得たものの分析例である。When the alkali-treated product thus obtained is leached with water, sodium zirconate is hydrolyzed to produce zirconium hydroxide and caustic soda. The solids obtained by removing sodium silicate and excess alkali by filtration are then water leached cakes. The water-leached cake mainly contains zirconium hydroxide, sodium zirconate, sodium zirconate silicate and unreacted zircon sand (Z
r sand). An example of the composition analysis of a water-leached cake is shown below. This uses caustic soda as an alkaline agent,
It is an analysis example of a reaction melt obtained by heating and melting at 50 ° C., which was obtained by filtering and washing after leaching with water.
【００１２】 含有されるＳｉＯ2の大部分は、ケイジルコン酸ソーダ
の成分である。該ケーク中のケイジルコン酸ソーダ含量
は、アルカリ処理の条件に左右されて増減する。通常、
該ケークの組成は、ＺｒＯ2＝３０〜５０ｗｔ％，Ｎａ2
Ｏ＝３〜１０ｗｔ％，ＳｉＯ2＝１〜８ｗｔ％の範囲に
ある。本発明は、この範囲の組成にも、またそれから外
れたものにも好適に適用することができる。[0012] Most of the contained SiO 2 is a component of sodium silicic acid silicate. The content of sodium silica zirconate in the cake increases or decreases depending on the conditions of alkali treatment. Normal,
The composition of the cake is ZrO 2 = 30-50 wt%, Na 2
It is in the range of O = 3 to 10 wt% and SiO 2 = 1 to 8 wt%. The present invention can be suitably applied to a composition within this range or a composition outside the range.
【００１３】水浸出ケークの塩酸抽出は、水浸出ケーク
に水を加えリパルプしてスラリーとし、その後に塩酸を
添加することによって行わねばならない。これに対し、
逆に、塩酸に水浸出ケーク又は水浸出ケークを水でリパ
ルプして得たスラリーを添加すると、生成したシリカの
ろ過性は悪く、溶解シリカ量も増す。最終の酸抽出液組
成がシリカの析出及びろ過性に大きな影響を与える。即
ち、水浸出ケークの組成及び量に対し添加する水および
塩酸の量が重要となる。Hydrochloric acid extraction of the water-leached cake must be carried out by adding water to the water-leaked cake to repulp it into a slurry and then adding hydrochloric acid. In contrast,
On the contrary, when a water-leached cake or a slurry obtained by repulping a water-leaked cake with water is added to hydrochloric acid, the filterability of the produced silica is poor and the amount of dissolved silica is increased. The final acid extract composition has a large effect on silica precipitation and filterability. That is, the amount of water and hydrochloric acid added to the composition and amount of the water leached cake is important.
【００１４】塩酸添加前に添加する、すなわちリパルプ
用の水の量は、塩酸添加の際にスラリーの撹拌を容易に
行うことができるものでなければならない。水の添加が
少なすぎると、塩酸添加前から撹拌が困難になるだけで
なく、塩酸添加に伴うシリカのゾル化によるスラリー粘
度の急上昇で撹拌不能になり易く、またろ過性も悪くな
る。しかし、この水の添加量が多すぎると、最終の酸抽
出液中のＺｒＯ2濃度及び遊離ＨＣｌ濃度が共に低くな
り、その結果、溶解シリカ量が多くなり、またシリカ粒
子のろ過性も悪くなる。以上の関係から水浸出ケークを
リパルプする水の量ならびに塩酸の濃度および量は、塩
酸抽出液の液相のＺｒＯ2換算濃度が９〜１６ｗｔ％と
なり、かつ、遊離ＨＣｌ濃度が１〜７ｗｔ％となるよう
に設定することを必須とする。その範囲内でも特に、Ｚ
ｒＯ2換算濃度は１１〜１５ｗｔ％、遊離ＨＣｌ濃度２
〜６ｗｔ％が好ましい。リパルプする水の添加量は、塩
酸添加前のスラリーのＺｒＯ2含量が２０〜３５ｗ％の
範囲内になるように行うのが好ましい。The amount of water added before the addition of hydrochloric acid, that is, the amount of water for repulping, must be such that the slurry can be easily stirred during the addition of hydrochloric acid. If the amount of water added is too small, it becomes difficult to stir even before the addition of hydrochloric acid, and it becomes difficult to stir due to the rapid increase in slurry viscosity due to the sol formation of silica accompanying the addition of hydrochloric acid, and the filterability also deteriorates. However, if the amount of this water added is too large, both the ZrO 2 concentration and the free HCl concentration in the final acid extract will be low, and as a result, the amount of dissolved silica will increase and the filterability of silica particles will also deteriorate. . From the above relationship, the amount of water for repulping the water-leached cake and the concentration and amount of hydrochloric acid are such that the ZrO 2 conversion concentration of the liquid phase of the hydrochloric acid extract is 9 to 16 wt% and the free HCl concentration is 1 to 7 wt%. It is essential to set so that Within that range, especially Z
rO 2 conversion concentration is 11 to 15 wt%, free HCl concentration is 2
-6 wt% is preferable. The amount of water to be repulped is preferably such that the ZrO 2 content of the slurry before addition of hydrochloric acid falls within the range of 20 to 35 w%.
【００１５】水浸出ケークスラリーへの塩酸添加は、本
発明の目的を遂行する上で、極めて重要となる。塩酸の
添加量は、水でリパルプされたスラリー中の水酸化ジル
コニウム，ジルコン酸ソーダおよびケイジルコン酸ソー
ダを分解するに必要な量、すなわち塩酸が前記の水浸出
ケーク中の組成ＺｒＯ2およびＮａ2Ｏとそれぞれ下式に
よる反応をするとした化学量論量と ＺｒＯ2＋２ＨＣｌ→ＺｒＯＣｌ2＋Ｈ2Ｏ Ｎａ2Ｏ＋２ＨＣｌ→２ＮａＣｌ＋Ｈ2Ｏ 上記の塩酸抽出液の遊離ＨＣｌ濃度を１〜７ｗｔ％とす
る過剰量との合計でなければならない。少なすぎると目
的物であるＺｒ分の抽出が不十分になるばかりか、シリ
カの析出率が低下し、シリカ粒子のろ過性も極度に悪化
する。反面、多すぎると溶解シリカ量が多くなる。The addition of hydrochloric acid to the water-leached cake slurry is extremely important in carrying out the purpose of the present invention. The amount of hydrochloric acid added depends on the amount required to decompose zirconium hydroxide, sodium zirconate and sodium zirconate silicate in the water-repulped slurry, that is, hydrochloric acid has the composition ZrO 2 and Na 2 in the water-leached cake. Stoichiometric amount for reaction with O according to the following formula, and ZrO 2 + 2HCl → ZrOCl 2 + H 2 O Na 2 O + 2HCl → 2NaCl + H 2 O Must be the sum of If the amount is too small, not only the target Zr component is insufficiently extracted, but also the deposition rate of silica is lowered and the filterability of silica particles is extremely deteriorated. On the other hand, if the amount is too large, the amount of dissolved silica increases.
【００１６】また、塩酸添加方法は、シリカの重合・ゲ
ル化の促進およびシリカ粒子のろ過性を支配する極めて
重要な因子となる。即ち、該スラリーを適度の撹拌のも
と、塩酸を１時間以上かけて添加するのがよい。スラリ
ーのｐＨが１０〜４、とくに１０〜６（塩酸添加開始前
のスラリーｐＨは１２以上である）の範囲内に下がった
時点で塩酸添加を一旦中断して、２０分間以上スラリー
ｐＨをその範囲に保持した後、引き続き塩酸添加を再開
し所定量の塩酸を添加することによって、さらにシリカ
の析出率を高くし（溶存率を低くし）、かつ、ろ過性を
向上することができる。この塩酸の添加を中断する方法
においても、塩酸の添加時間はｐＨ保持時間を除き１時
間以上かけて添加するのが好ましい。添加が１時間より
短いと、溶解シリカ量が高くなり、シリカ粒子のろ過性
も低下する。この添加時間は長いほどその効果は高い
が、あまり長くしても効果の向上は望めず、生産性の点
から３時間以内とするのが望ましい。The method of adding hydrochloric acid is an extremely important factor that controls the polymerization / gelation of silica and the filterability of silica particles. That is, it is preferable that hydrochloric acid be added over 1 hour or more with appropriate stirring of the slurry. When the pH of the slurry falls within the range of 10 to 4, particularly 10 to 6 (the pH of the slurry before the addition of hydrochloric acid is 12 or more), the addition of hydrochloric acid is temporarily interrupted and the slurry pH is kept in the range for 20 minutes or more. After that, the addition of hydrochloric acid is restarted and a predetermined amount of hydrochloric acid is added to further increase the precipitation rate of silica (lower the dissolution rate) and improve the filterability. Also in the method of interrupting the addition of hydrochloric acid, it is preferable that the addition time of hydrochloric acid is 1 hour or more except the pH holding time. When the addition is shorter than 1 hour, the amount of dissolved silica becomes high and the filterability of silica particles also deteriorates. The longer the addition time is, the higher the effect is. However, if the addition time is too long, the effect cannot be expected to be improved. From the viewpoint of productivity, the addition time is preferably within 3 hours.
【００１７】塩酸添加時のスラリー温度は、反応熱等に
よる温度上昇があるため、塩酸添加終了時点で６０〜８
０℃になるように、スタート時のスラリー温度を調節し
ておくのがよい。６０〜８０℃の範囲で反応およびシリ
カの重合・ゲル化がよく進行するからである。装置が保
温されている場合、浸出ケークスラリー組成にもよる
が、通常はスタート時のスラリー温度を常温〜５０℃に
設定しておけば、加熱，冷却することなくほぼ上記の温
度に達する。Since the temperature of the slurry when hydrochloric acid is added rises due to the heat of reaction or the like, 60 to 8 at the end of the addition of hydrochloric acid.
It is advisable to adjust the slurry temperature at the start so that it becomes 0 ° C. This is because the reaction and the polymerization / gelation of silica proceed well in the range of 60 to 80 ° C. When the apparatus is kept warm, it usually depends on the composition of the leaching cake slurry, but if the slurry temperature at the start is set to room temperature to 50 ° C., the above temperature is reached without heating and cooling.
【００１８】塩酸の添加が終了したら、スラリーは温度
を８０℃以上に保持し、４時間以上撹拌を継続すること
が好ましい。この熟成によって、ジルコニウム分の抽出
およびシリカ分の重合・ゲル化がほぼ完了する。温度が
低すぎるとＺｒ分の抽出およびシリカ分の重合・ゲル化
が不十分となるので８０℃以上が好ましく、９０℃以上
がより効果的である。保持時間が長いほどジルコニウム
分の抽出とシリカ分の重合・ゲル化が進むので、４時間
以上が好ましい。より好ましくは６時間以上であり、長
い方には制限はなく任意に決めればよい。この温度保持
に引き続き、スラリーは７０℃以下に冷却するのが好ま
しい。この冷却は溶解シリカ量を下げる上で効果的であ
る。温度が低いほどシリカの溶解度が下がるので７０℃
以下が好ましく、より好ましくは６５℃以下である。し
かし、下げすぎるとＺＯＣが析出したり、スラリー粘度
が高くなってろ過性が低下するのでＺＯＣの溶解度およ
び液物性で決めればよく、通常５０℃までが操作性の点
で好ましい。After the addition of hydrochloric acid is completed, it is preferable to keep the temperature of the slurry at 80 ° C. or higher and continue stirring for 4 hours or longer. By this aging, the extraction of zirconium and the polymerization / gelling of silica are almost completed. If the temperature is too low, the extraction of the Zr component and the polymerization / gelling of the silica component will be insufficient, so 80 ° C or higher is preferable, and 90 ° C or higher is more effective. The longer the holding time is, the more the zirconium content is extracted and the silica content is polymerized and gelled. It is more preferably 6 hours or more, and there is no limit to the longer one and it may be arbitrarily determined. Following this temperature maintenance, the slurry is preferably cooled to 70 ° C or lower. This cooling is effective in reducing the amount of dissolved silica. The lower the temperature, the lower the solubility of silica, so 70 ℃
The following is preferable, and 65 ° C. or less is more preferable. However, if too low, ZOC precipitates or the slurry viscosity increases and the filterability decreases, so it may be determined by the solubility and liquid physical properties of ZOC, and usually 50 ° C. is preferable in terms of operability.
【００１９】冷却後固液分離を実施して、シリカおよび
ジルコニア砂を除去する。固液分離は、フイルタープレ
ス，減圧吸引ろ過機，プレコート加圧ろ過機等の通常の
ろ過手段によって実施すればよい。ろ過機は回分式，連
続式いずれも使用することができる。After cooling, solid-liquid separation is carried out to remove silica and zirconia sand. Solid-liquid separation may be carried out by an ordinary filtering means such as a filter press, a vacuum suction filter, a precoat pressure filter, or the like. The filter can be either a batch type or a continuous type.
【００２０】また、高分子凝集剤の添加により、より効
果的に固液分離を実施することができる。高分子凝集剤
としては、カチオン性のポリメタクリル酸エステル，ポ
リアミン、ノニオン性のポリアクリルアミド，ポリエチ
レンオキサイドなどをあげることができる。高分子凝集
剤は、特に制限はないが、ＳｉＯ2１００重量部に対し
て０．５〜５重量部添加するのが好ましい。添加方法と
しては、分散性の面から水溶液にして添加するのがよ
い。添加時期は固液分離直前が好ましい。Further, solid-liquid separation can be more effectively carried out by adding a polymer flocculant. Examples of the polymer flocculant include cationic polymethacrylic acid ester, polyamine, nonionic polyacrylamide, polyethylene oxide and the like. The polymer coagulant is not particularly limited, but it is preferable to add 0.5 to 5 parts by weight to 100 parts by weight of SiO 2 . As an addition method, an aqueous solution is preferably added from the viewpoint of dispersibility. The time of addition is preferably immediately before solid-liquid separation.
【００２１】[0021]
【作用】本発明における塩酸抽出液中のシリカの析出率
が高くかつ析出シリカ粒子のろ過性に優れる理由は、以
下の様に推定している。The reason for the high deposition rate of silica in the hydrochloric acid extract and the excellent filterability of the precipitated silica particles in the present invention is presumed as follows.
【００２２】本発明では、液性をアルカリ側から酸性側
に適度に変化させることで、シリカの重合ならびに生成
ゾルの粒子成長および凝集を大幅に促進する条件が満た
され、それによって最終的に得られるシリカの析出粒子
のろ過性が良くなり、溶解シリカ量も少なくなるものと
考えられる。In the present invention, by appropriately changing the liquidity from the alkaline side to the acidic side, the conditions for significantly promoting the polymerization of silica and the particle growth and agglomeration of the produced sol are satisfied. It is considered that the filterability of precipitated silica particles is improved and the amount of dissolved silica is reduced.
【００２３】[0023]
【発明の効果】本発明によれば、水浸出ケークより、溶
解シリカ量が少なくかつろ過性のよい析出シリカ粒子を
含有する塩酸抽出液がえられ、それによって高品質のジ
ルコニウム塩化物水溶液を効果的かつ効率的に製造する
ことができる。INDUSTRIAL APPLICABILITY According to the present invention, a hydrochloric acid extract containing precipitated silica particles having a smaller amount of dissolved silica and good filterability can be obtained from a water leaching cake, whereby a high-quality zirconium chloride aqueous solution can be obtained. Can be manufactured efficiently and efficiently.
【００２４】[0024]
【実施例】以下、本発明を実施例によりさらに説明する
が、本発明はこれらに限定されるものではない。EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto.
【００２５】実施例および比較例に用いた水浸出ケーク
の組成分析値を以下に示す。The compositional analysis values of the water-leached cakes used in Examples and Comparative Examples are shown below.
【００２６】ＺｒＯ2＝３７．４ｗｔ％，Ｎａ2Ｏ＝７．
５ｗｔ％，ＳｉＯ2＝４．５ｗｔ％，Ｈ2Ｏ＝４１．５ｗ
ｔ％，未反応Ｚｒ砂＝９．１ｗｔ％。ZrO 2 = 37.4 wt%, Na 2 O = 7.
5wt%, SiO 2 = 4.5wt% , H 2 O = 41.5w
t%, unreacted Zr sand = 9.1 wt%.
【００２７】実施例 １ ２リットルのガラス製セパラブルフラスコに、上記組成
を有する水浸出ケーク１０００ｇに水６８０ｇを加えス
ラリーとした。温度は３４℃で、スラリーｐＨ＝１３．
４であった。撹拌を行いながら３５ｗｔ％塩酸１２１５
ｇを１６．２ｇ／ｍｉｎの流速にて添加した。スラリー
ｐＨが６．０になった時、塩酸の添加を止め３０分間撹
拌のみ行った後、再び塩酸添加を再開した。塩酸添加が
終了した時点でスラリー温度は９０℃とした。９０℃に
保持しながら８時間撹拌した後、スラリー温度を６０℃
に下げた。このスラリーに０．５ｗｔ％ポリエチレンオ
キサイド（以下、ＰＥＯという）水溶液１３５ｇを添加
し、２時間後ガラス繊維製ろ紙を装着したブフナーロー
ト（内径２０ｃｍ）で吸引ろ過した。ろ過ケークを温水
５８５ｍｌで洗浄し、シリカ粒子および未反応Ｚｒ砂か
らなるケーク４６７ｇと、ＺｒＯ2＝１１．７ｗｔ％，
ＮａＣｌ＝４．４ｗｔ％，遊離ＨＣｌ＝３．６ｗｔ％、
およびＳｉＯ2＝０．０１９ｗｔ％からなるジルコニウ
ム塩化物水溶液３１４３ｇを回収した。Example 1 In a 2 liter glass separable flask, 680 g of water was added to 1000 g of the water-leaked cake having the above composition to prepare a slurry. The temperature is 34 ° C. and the slurry pH is 13.
It was 4. 35 wt% hydrochloric acid 1215 while stirring
g was added at a flow rate of 16.2 g / min. When the pH of the slurry reached 6.0, the addition of hydrochloric acid was stopped, stirring was continued for 30 minutes, and then the addition of hydrochloric acid was restarted. When the addition of hydrochloric acid was completed, the slurry temperature was 90 ° C. After stirring at 90 ° C for 8 hours, the slurry temperature was changed to 60 ° C.
Lowered to. To this slurry, 135 g of a 0.5 wt% polyethylene oxide (hereinafter referred to as PEO) aqueous solution was added, and after 2 hours, suction filtration was performed with a Buchner funnel (inner diameter 20 cm) equipped with a glass fiber filter paper. The filter cake was washed with 585 ml of warm water to obtain 467 g of a cake composed of silica particles and unreacted Zr sand, ZrO 2 = 11.7 wt%,
NaCl = 4.4 wt%, free HCl = 3.6 wt%,
Then, 3143 g of a zirconium chloride aqueous solution consisting of SiO 2 = 0.019 wt% was recovered.
【００２８】比較例 １ ３５ｗｔ％塩酸１２１５ｇに水浸出ケーク１０００ｇを
水６８０ｇでリパルプしたスラリーを添加し、９０℃で
８時間撹拌した後６０℃に冷却し、０．５ｗｔ％ＰＥＯ
水溶液１３５ｇを添加し、実施例１と同一条件で該スラ
リーのろ過を行ったところ、およそ２０ｇの液が得られ
た時点でろ過不能となった。Comparative Example 1 To 1215 g of 35 wt% hydrochloric acid, a slurry prepared by repulping 1000 g of water-leached cake with 680 g of water was added, stirred at 90 ° C. for 8 hours, and then cooled to 60 ° C. to obtain 0.5 wt% PEO.
When 135 g of an aqueous solution was added and the slurry was filtered under the same conditions as in Example 1, filtration became impossible when approximately 20 g of a liquid was obtained.
【００２９】実施例 ２〜６， 比較例 ２，３ 表１に示す条件で、ただしそこに示す以外の条件は実施
例１と同一にして、実施した。その結果を表２に示す。Examples 2 to 6 and Comparative Examples 2 and 3 were carried out under the conditions shown in Table 1 except that the conditions other than those shown therein were the same as in Example 1. The results are shown in Table 2.
【００３０】[0030]
【表１】 [Table 1]
【００３１】[0031]
【表２】 [Table 2]
Claims (6)
出処理し、ろ過して得た水浸出ケークを塩酸によって抽
出してジルコニウム塩化物水溶液を製造する方法におい
て、該ケークに水を加えてスラリーとし、該スラリーを
撹拌しつつこれに塩酸を、得られる懸濁液の液相におけ
るジルコニウム塩化物のＺｒＯ2換算濃度が９〜１６ｗ
ｔ％となり、かつ、遊離ＨＣｌ濃度が１〜７ｗｔ％とな
るように加え、次いでろ過することを特徴とする、ジル
コニウム塩化物水溶液の製造方法。1. A method for producing an aqueous zirconium chloride solution by extracting a water-leached cake obtained by leaching an alkali-treated zircon sand with water and filtering the mixture, and adding water to the cake to form a slurry. The hydrochloric acid was added to the slurry while stirring, and the ZrO 2 conversion concentration of zirconium chloride in the liquid phase of the obtained suspension was 9 to 16 w.
A method for producing a zirconium chloride aqueous solution, which comprises adding t HCl at a free HCl concentration of 1 to 7 wt% and then filtering.
項１記載の方法。2. The method according to claim 1, wherein the hydrochloric acid is added for 1 hour or more.
時点で２０分間以上中断した後再開する、請求項１また
は２記載の方法。3. The method according to claim 1 or 2, wherein the addition of hydrochloric acid is resumed after being interrupted for 20 minutes or longer at a slurry pH of 4 to 10.
間以上熟成する、請求項１〜３いずれかの項記載の方
法。4. The method according to claim 1, wherein after the addition of hydrochloric acid, the slurry is aged at 80 ° C. or higher for 4 hours or longer.
℃以下に冷却する、請求項１〜４いずれかの項記載の方
法。5. 70% before filtering the slurry after addition of hydrochloric acid
The method according to any one of claims 1 to 4, wherein the method is cooled to ℃ or less.
分子凝集剤を添加する請求項１〜５いずれかの項記載の
方法。6. The method according to claim 1, wherein a polymer flocculant is added before filtering the slurry after addition of hydrochloric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27836692A JP3427211B2 (en) | 1992-10-16 | 1992-10-16 | Method for producing zirconium chloride aqueous solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27836692A JP3427211B2 (en) | 1992-10-16 | 1992-10-16 | Method for producing zirconium chloride aqueous solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06127944A true JPH06127944A (en) | 1994-05-10 |
| JP3427211B2 JP3427211B2 (en) | 2003-07-14 |
Family
ID=17596345
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27836692A Expired - Fee Related JP3427211B2 (en) | 1992-10-16 | 1992-10-16 | Method for producing zirconium chloride aqueous solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3427211B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU685018B2 (en) * | 1995-06-21 | 1998-01-08 | Korea Research Institute Of Chemical Technology | Process for preparing high-purity zirconium oxychloride crystals |
| WO2005035446A1 (en) * | 2003-10-14 | 2005-04-21 | Daiichi Kigenso Kagaku Kogyo Co., Ltd. | Method for producing aqueous solution of chlorination product of zirconium |
| WO2017119374A1 (en) * | 2016-01-05 | 2017-07-13 | 住友電気工業株式会社 | Method for separating metallic component |
| EP3067320A4 (en) * | 2014-01-16 | 2017-08-09 | Daiichi Kigenso Kagaku Kogyo Co., Ltd. | Method for producing aqueous zirconium chloride solution |
| CN110885930A (en) * | 2019-11-18 | 2020-03-17 | 中国科学院过程工程研究所 | Resource utilization method of zirconium oxychloride crystallization mother liquor |
-
1992
- 1992-10-16 JP JP27836692A patent/JP3427211B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU685018B2 (en) * | 1995-06-21 | 1998-01-08 | Korea Research Institute Of Chemical Technology | Process for preparing high-purity zirconium oxychloride crystals |
| WO2005035446A1 (en) * | 2003-10-14 | 2005-04-21 | Daiichi Kigenso Kagaku Kogyo Co., Ltd. | Method for producing aqueous solution of chlorination product of zirconium |
| AU2004279711B2 (en) * | 2003-10-14 | 2009-05-28 | Daiichi Kigenso Kagaku Kogyo Co., Ltd. | Method for producing aqueous solution of chlorination product of zirconium |
| EP3067320A4 (en) * | 2014-01-16 | 2017-08-09 | Daiichi Kigenso Kagaku Kogyo Co., Ltd. | Method for producing aqueous zirconium chloride solution |
| WO2017119374A1 (en) * | 2016-01-05 | 2017-07-13 | 住友電気工業株式会社 | Method for separating metallic component |
| US11066724B2 (en) | 2016-01-05 | 2021-07-20 | Sumitomo Electric Industries, Ltd. | Method for separating metal components |
| CN110885930A (en) * | 2019-11-18 | 2020-03-17 | 中国科学院过程工程研究所 | Resource utilization method of zirconium oxychloride crystallization mother liquor |
| CN110885930B (en) * | 2019-11-18 | 2021-03-09 | 中国科学院过程工程研究所 | Resource utilization method of zirconium oxychloride crystallization mother liquor |
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| Publication number | Publication date |
|---|---|
| JP3427211B2 (en) | 2003-07-14 |
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