JP6260419B2 - Method for producing aqueous calcium chloride solution - Google Patents
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Description
本発明は、不純物を含む塩酸及び／又はカルシウム源から固液分離が容易であり、且つ、不純物を効率的に除去できる塩化カルシウム水溶液の製造方法に関する発明である。 The present invention relates to a method for producing an aqueous calcium chloride solution that can be easily separated from a hydrochloric acid and / or calcium source containing impurities and can efficiently remove impurities.
塩化カルシウム水溶液は、石膏等のカルシウム化合物製造原料や排水中フッ素の除去剤として、また道路の凍結防止剤や冷凍機用ブライン等として有用な無機化合物である。この塩化カルシウム水溶液の製造方法は、固液分離が容易であり、効率的に不純物を除去する事が要求される。 Calcium chloride aqueous solution is an inorganic compound useful as a raw material for producing calcium compounds such as gypsum and a fluorine removing agent in wastewater, as a road antifreeze, a brine for refrigerators, and the like. This method for producing an aqueous calcium chloride solution requires easy solid-liquid separation and is required to efficiently remove impurities.
例えば、塩化カルシウム水溶液を石膏の製造原料とする場合、これを硫酸ナトリウムと反応させるが、この塩化カルシウム中に不純物が含まれると、析出させた石膏の純度低下や着色、更には石膏の結晶成長不良の原因になることがあった（例えば、特許文献１）。 For example, when an aqueous calcium chloride solution is used as a raw material for producing gypsum, it is reacted with sodium sulfate. If impurities are contained in this calcium chloride, the purity of the precipitated gypsum is reduced or colored, and further the crystal growth of gypsum. There was a case of causing a defect (for example, Patent Document 1).
一旦純度の高いオキシ塩化カルシウムの結晶を析出させて、分離した後、水に溶解させて再度濾過することで高純度な塩化カルシウム水溶液を製造する方法が開示されている（例えば、特許文献２）。確かに、この方法によって高純度の塩化カルシウム水溶液を製造することができるが、この方法は工程が複雑で生産性が良くなく、製造コストが嵩むといった課題があった。 A method of producing a high-purity calcium chloride aqueous solution by precipitating and separating high-purity calcium oxychloride crystals once, dissolving in water, and filtering again is disclosed (for example, Patent Document 2). . Certainly, a high-purity calcium chloride aqueous solution can be produced by this method, but this method has a problem that the process is complicated, the productivity is not good, and the production cost is increased.
一方、石灰石を固定床に充填し、この固定床の下部から塩酸を連続的に供給することで塩化カルシウム水溶液を製造する方法が開示されている（例えば、特許文献３）。確かにこの方法は安価な石灰石を原料として、効率良く塩化カルシウム水溶液を製造することができる。しかしながら、この方法で得られる塩化カルシウム水溶液には未反応の塩酸が残存するため、マグネシウムやリン、フッ素などの酸可溶性不純物を多く含む。その為、後工程にて石灰乳などのアルカリ剤を用いて中和し、製品化されるが、アルカリ剤を添加すると石灰石や塩酸に含まれる前記無機不純物が微細な粒子を形成して沈殿し、濾過等の固液分離によって容易に除去できないため、大きな濾過面積が必要となり、設備の大型化を招き、設備投資額が嵩むといった課題があった。 On the other hand, a method for producing a calcium chloride aqueous solution by filling limestone into a fixed bed and continuously supplying hydrochloric acid from the lower part of the fixed bed is disclosed (for example, Patent Document 3). Certainly, this method can efficiently produce an aqueous calcium chloride solution using inexpensive limestone as a raw material. However, since unreacted hydrochloric acid remains in the calcium chloride aqueous solution obtained by this method, it contains a large amount of acid-soluble impurities such as magnesium, phosphorus and fluorine. For this reason, it is neutralized with an alkaline agent such as lime milk in a later step, and commercialized. However, when an alkaline agent is added, the inorganic impurities contained in limestone and hydrochloric acid form fine particles and precipitate. Since it cannot be easily removed by solid-liquid separation such as filtration, there is a problem that a large filtration area is required, leading to an increase in equipment size and an increase in capital investment.
本発明は、上記の背景技術に鑑みてなされたものであり、その目的は、固液分離が容易、且つ、効率的に不純物を除去する塩化カルシウム水溶液の製造方法を提供することにある。 The present invention has been made in view of the above-described background art, and an object of the present invention is to provide a method for producing an aqueous calcium chloride solution that facilitates solid-liquid separation and efficiently removes impurities.
本発明者らは、不純物を含む塩酸及び／又はカルシウム源を原料とした塩化カルシウム水溶液の製造方法について、鋭意検討した結果、カルシウム塩を析出させ、得られた塩化カルシウムのスラリーにアルカリ剤を添加し、そのｐＨを６〜１２の範囲とし、その塩化カルシウムのスラリーを固液分離すると、固液分離が容易で、且つ、塩化カルシウムスラリー中の不純物を効率的に除去できることを見い出し、本発明を完成するに至った。 As a result of intensive studies on a method for producing an aqueous calcium chloride solution using hydrochloric acid and / or calcium sources containing impurities as raw materials, the present inventors have precipitated calcium salts and added an alkali agent to the obtained calcium chloride slurry. Then, when the pH is in the range of 6 to 12 and the calcium chloride slurry is solid-liquid separated, it is found that the solid-liquid separation is easy and impurities in the calcium chloride slurry can be efficiently removed. It came to be completed.
即ち本発明は、以下に示すとおりの塩化カルシウム水溶液の製造方法である。
［１］以下の工程を含む塩化カルシウム水溶液の製造方法。
That is, this invention is a manufacturing method of calcium chloride aqueous solution as shown below.
[1] A method for producing an aqueous calcium chloride solution comprising the following steps.
工程１：塩酸とカルシウム源とを反応させる工程
工程２：工程１で得られた未反応塩酸を含む塩化カルシウム水溶液に薬剤を添加し、平均一次粒子径が１〜１０μｍのカルシウム塩を析出させる工程
工程３：工程２で得られたスラリーにアルカリ剤を添加し、そのｐＨを６〜１２の範囲とする工程
工程４：工程３で得られたスラリーを固液分離し、当該スラリー中の固形分を分離除去する工程
［２］工程２のカルシウム塩が結晶性カルシウム塩である上記［１］に記載の塩化カルシウム水溶液の製造方法。
［３］工程１で使用されるカルシウム源が石灰石、石灰乳、消石灰、及び生石灰の群から選ばれる１種以上であることを特徴とする上記［１］又は［２］に記載の塩化カルシウム水溶液の製造方法。
［４］工程１において、塩酸及びカルシウム源以外に、マグネシウム、フッ素、及びリン群から選ばれる少なくとも１種以上の化合物が含まれることを特徴とする上記［１］乃至［３］のいずれかに記載の塩化カルシウム水溶液の製造方法。
［５］工程２で析出させる平均一次粒子径が１〜１０μｍのカルシウム塩が炭酸カルシウム及び硫酸カルシウムの群から選ばれる少なくとも１種以上であることを特徴とする上記［１］乃至［４］のいずれかに記載の塩化カルシウム水溶液の製造方法。
［６］工程３で使用されるアルカリ剤が、石灰乳、及び消石灰の群から選ばれる１種以上であることを特徴とする上記［１］乃至［５］のいずれかに記載の塩化カルシウム水溶液の製造方法。
［７］工程４の固液分離が濾過であることを特徴とする上記［１］乃至［６］のいずれかに記載の塩化カルシウム水溶液の製造方法。
Step 1: Step of reacting hydrochloric acid and calcium source Step 2: Step of adding a chemical to the calcium chloride aqueous solution containing unreacted hydrochloric acid obtained in Step 1 to precipitate a calcium salt having an average primary particle diameter of 1 to 10 μm. Step 3: A step of adding an alkaline agent to the slurry obtained in Step 2 to adjust its pH to a range of 6 to 12. Step 4: Solid-liquid separation of the slurry obtained in Step 3 and solid content in the slurry [2] The method for producing a calcium chloride aqueous solution according to the above [1], wherein the calcium salt in Step 2 is a crystalline calcium salt.
[3] The calcium chloride aqueous solution according to the above [1] or [2], wherein the calcium source used in step 1 is at least one selected from the group consisting of limestone, lime milk, slaked lime, and quicklime. Manufacturing method.
[4] In any one of the above [1] to [3], in Step 1, in addition to hydrochloric acid and a calcium source, at least one compound selected from the group consisting of magnesium, fluorine, and phosphorus is included. The manufacturing method of calcium chloride aqueous solution of description.
[5] The above [1] to [4], wherein the calcium salt having an average primary particle size of 1 to 10 μm precipitated in step 2 is at least one selected from the group consisting of calcium carbonate and calcium sulfate. The manufacturing method of the calcium chloride aqueous solution in any one.
[6] The aqueous calcium chloride solution according to any one of the above [1] to [5], wherein the alkaline agent used in step 3 is at least one selected from the group of lime milk and slaked lime. Manufacturing method.
[7] The method for producing an aqueous calcium chloride solution according to any one of the above [1] to [6], wherein the solid-liquid separation in step 4 is filtration.
本発明の方法によれば、不純物を含む塩化カルシウム水溶液から、固液分離が容易で、且つ、不純物を効果的かつ効率的に除去できる。又、その時の固液分離が容易であることから設備をコンパクトにでき、設置面積を少なく、設備投資額を抑えることができる。 According to the method of the present invention, solid-liquid separation is easy from an aqueous calcium chloride solution containing impurities, and impurities can be effectively and efficiently removed. Moreover, since the solid-liquid separation at that time is easy, the equipment can be made compact, the installation area can be reduced, and the capital investment can be suppressed.
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明において工程１は、塩酸とカルシウム源を反応させる工程である。用いる塩酸については特に限定しない。具体的には、塩素と水素から製造される合成塩酸や、化学プラントから副生する塩酸、塩化水素ガス等を例示でき、いずれでも構わない。好ましくは、安価で資源の有効利用につながる、化学プラント等から副生する塩酸である。塩酸の濃度は、特に限定しない。濃度が高い程、塩化カルシウムの濃度を高くできるので良いが、高すぎると塩化水素の揮発が顕著となりハンドリングが難しくなる。好ましくは１５〜３８重量％、より好ましくは２０〜３７重量％である。本発明に用いる塩酸には不純物が含まれていても構わない。不純物は、塩酸の製造過程で混入する場合や、配管や貯槽等の材質からの混入もあるが、いずれであっても構わない。不純物の種類についても特に限定しない。具体的にはマグネシウム、リン、フッ素、鉄、ニッケル、クロム、ケイ素、アルミニウム等の化合物等を例示できる。これら不純物の全部又は一部は工程２〜工程４にて除去できる。除去容易な不純物は、マグネシウム、リン、フッ素、鉄の化合物である。又、カルシウム源は、塩酸と反応して塩化カルシウムを生成できるものであれば特に限定しない。具体的には、石灰石、石灰乳、消石灰、生石灰等を挙げることができ、なかでも入手が容易で安価な石灰石が好ましい。又、カルシウム源に不純物が含まれることがあっても構わない。不純物の種類については特に制限せず、具体的には、マグネシウム、リン、フッ素、鉄、アルミニウム、クロム、ケイ素、イオウなどの化合物を挙げることができる。これら不純物の全部又は一部は工程２〜工程４にて除去できる。その除去の容易な不純物は、マグネシウム、リン、フッ素、鉄の化合物である。 In the present invention, step 1 is a step of reacting hydrochloric acid with a calcium source. The hydrochloric acid to be used is not particularly limited. Specific examples include synthetic hydrochloric acid produced from chlorine and hydrogen, hydrochloric acid by-produced from a chemical plant, hydrogen chloride gas, and the like. Preferably, it is hydrochloric acid by-produced from a chemical plant or the like, which is inexpensive and leads to effective use of resources. The concentration of hydrochloric acid is not particularly limited. The higher the concentration, the higher the calcium chloride concentration can be. However, if the concentration is too high, volatilization of hydrogen chloride becomes remarkable and handling becomes difficult. Preferably it is 15 to 38 weight%, More preferably, it is 20 to 37 weight%. The hydrochloric acid used in the present invention may contain impurities. Impurities may be mixed during the manufacturing process of hydrochloric acid or mixed from materials such as pipes and storage tanks, but any of them may be used. There are no particular limitations on the type of impurities. Specific examples include compounds such as magnesium, phosphorus, fluorine, iron, nickel, chromium, silicon, and aluminum. All or part of these impurities can be removed in steps 2 to 4. Impurities that can be easily removed are compounds of magnesium, phosphorus, fluorine, and iron. The calcium source is not particularly limited as long as it can react with hydrochloric acid to produce calcium chloride. Specific examples include limestone, lime milk, slaked lime, quicklime, etc. Among them, limestone that is easily available and inexpensive is preferable. Further, impurities may be contained in the calcium source. There are no particular restrictions on the type of impurities, and specific examples include compounds such as magnesium, phosphorus, fluorine, iron, aluminum, chromium, silicon, and sulfur. All or part of these impurities can be removed in steps 2 to 4. The impurities that can be easily removed are magnesium, phosphorus, fluorine, and iron compounds.
このような塩酸とカルシウム源を反応させて、塩化カルシウムの水溶液を得る。尚、この水溶液は塩酸不溶の懸濁物質（ＳＳ）を含むこともある。又、本工程では、未反応の塩酸を残すことを必須とする。未反応の塩酸は工程２〜工程３にて一部又は全部を薬剤やアルカリ剤の添加にて中和処理し、ｐＨ６〜１２とする。工程１で反応させた後の未反応の塩酸濃度は特に限定しない。塩酸濃度が高すぎると工程２〜工程３での中和処理に要する薬剤やアルカリ剤の使用量が多くなり、低すぎると工程１の反応に時間を要し、反応器が大型化して設備費が嵩む。好ましい塩酸濃度は０．０１〜５重量％、より好ましくは０．０２〜１重量％、更には０．０５〜０．５重量％が好ましい。反応の方式は、回分式であっても、連続式であっても構わない。又、反応装置の形式についても特に限定しないが、連続式では、特開平０９−０８６９２６号公報に開示されている方法が好ましく効率良く実施できる。即ち、該方法は固定床に石灰石等の塊状のカルシウム源を充填し、下部から連続的に塩酸を供給し、上部から連続的に塩化カルシウム水溶液を流出させる方法であり、生産効率が高く、運転操作が容易である。回分式の場合は、反応効率を高める目的で、カルシウム源を予め粉砕機等によって細かくし、撹拌槽にて反応させる方法等が好適に実施できる。 By reacting such hydrochloric acid with a calcium source, an aqueous solution of calcium chloride is obtained. This aqueous solution may contain a suspended substance (SS) insoluble in hydrochloric acid. In this step, it is essential to leave unreacted hydrochloric acid. Unreacted hydrochloric acid is partially or entirely neutralized by adding chemicals or alkaline agents in Steps 2 to 3 to pH 6-12. The concentration of unreacted hydrochloric acid after the reaction in step 1 is not particularly limited. If the concentration of hydrochloric acid is too high, the amount of chemicals and alkali agents required for the neutralization process in steps 2 to 3 will increase. If it is too low, the reaction in step 1 will take time, and the reactor will be enlarged, resulting in equipment costs. Is bulky. The hydrochloric acid concentration is preferably 0.01 to 5% by weight, more preferably 0.02 to 1% by weight, and even more preferably 0.05 to 0.5% by weight. The reaction system may be a batch system or a continuous system. Also, the type of the reaction apparatus is not particularly limited, but in the continuous type, the method disclosed in JP-A-09-086926 is preferably carried out efficiently. In other words, the method is a method in which a fixed bed is filled with a massive calcium source such as limestone, hydrochloric acid is continuously supplied from the lower part, and the aqueous calcium chloride solution is continuously discharged from the upper part. Easy to operate. In the case of a batch system, for the purpose of increasing the reaction efficiency, a method of making the calcium source fine in advance with a pulverizer or the like and reacting in a stirring tank can be suitably implemented.
工程２では、工程１で得られた塩化カルシウムと残存塩酸からなる水溶液に、薬剤を添加し、カルシウム塩を析出させる。ここでは、添加した薬剤の陰イオンと塩化カルシウム水溶液中のカルシウムイオンを反応させて難溶性でカルシウム塩を析出させる。この際に、カルシウム塩の平均一次粒子径を１〜１０μｍに成長したカルシウム塩とすることで、析出した不純物の難溶性物質の粒子が微細であるので、固液分離が容易となる。さらに、そのカルシウム塩を結晶性とすることにより、不純物の難溶性物質の粒子がカルシウム塩の表面に付着又は吸着し、固液分離がさらに容易となり、更に好ましい。 In step 2, a chemical is added to the aqueous solution composed of calcium chloride and residual hydrochloric acid obtained in step 1 to precipitate a calcium salt. Here, the anion of the added drug is reacted with calcium ions in the calcium chloride aqueous solution to precipitate a calcium salt that is hardly soluble. At this time, by using a calcium salt having an average primary particle diameter of 1 to 10 μm as the average primary particle diameter of the calcium salt, the particles of the hardly soluble substance of the precipitated impurities are fine, so that solid-liquid separation is facilitated. Further, by making the calcium salt crystalline, it is more preferable that particles of the poorly soluble substance of impurities adhere or adsorb on the surface of the calcium salt, and solid-liquid separation becomes easier.
この時、用いる薬剤は、析出させるカルシウム塩と不純物の難溶性物質の固液分離が容易であれば良く、特に限定しない。具体的には炭酸塩、重炭酸塩、硫酸塩などを例示できる。これらはカルシウムイオンと反応し固液分離が容易な炭酸カルシウムや硫酸カルシウムの沈殿を生成する。更に好ましい薬剤はｐＨを高めることができ、工程３でのアルカリ剤の必要量を低減できる炭酸塩、重炭酸塩である。この工程でｐＨを高めると、塩化カルシウム水溶液に含まれる不純物の種類や濃度によっては、不純物が析出することもあるが、構わない。不純物は析出したカルシウム塩の表面に析出したり、吸着したりすることがあるが、このことで、工程４での固液分離がより容易となるので、本発明の好ましい態様の一つとなる。工程２の反応形式は特に限定しない。運転操作性が良く、析出結晶の成長が良いことから撹拌槽方式が好ましい。 At this time, the agent to be used is not particularly limited as long as it allows easy solid-liquid separation of the precipitated calcium salt and the poorly soluble substance of impurities. Specific examples include carbonates, bicarbonates, sulfates, and the like. These react with calcium ions to produce precipitates of calcium carbonate and calcium sulfate that can be easily separated into solid and liquid. Further preferred agents are carbonates and bicarbonates that can raise the pH and reduce the required amount of alkaline agent in step 3. If the pH is increased in this step, impurities may precipitate depending on the type and concentration of impurities contained in the calcium chloride aqueous solution, but this is not a problem. Impurities may be deposited or adsorbed on the surface of the precipitated calcium salt, and this facilitates solid-liquid separation in step 4 and is one of the preferred embodiments of the present invention. The reaction mode of step 2 is not particularly limited. The stirring tank method is preferred because of good operation operability and good growth of precipitated crystals.
工程３では、工程２で得られたスラリーにアルカリ剤を添加し、そのｐＨを６〜１２の範囲とする。アルカリ剤の種類は、特に限定しない。具体的には、石灰石、石灰乳、消石灰、生石灰、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、アンモニア等を例示できる。好ましいアルカリ剤はｐＨを６〜１２とする際のコントロールが容易で、薬剤コストが安価な石灰乳、消石灰、水酸化ナトリウムである。より好ましくは石灰乳、消石灰である。ｐＨを高めることで原料の塩酸やカルシウム源に含まれる不純物の全部又は一部が難溶性物質として析出する。工程２で析出したカルシウム塩の平均一次粒子径を１〜１０μｍとすることで、ここで析出する難溶性物質の粒子が微細でも、その固液分離が容易であることが本発明の特徴である。 In step 3, an alkaline agent is added to the slurry obtained in step 2, and the pH is set in the range of 6-12. The kind of alkali agent is not particularly limited. Specific examples include limestone, lime milk, slaked lime, quicklime, sodium hydroxide, potassium hydroxide, lithium hydroxide, and ammonia. Preferred alkaline agents are lime milk, slaked lime, and sodium hydroxide, which are easy to control when the pH is adjusted to 6 to 12, and have a low drug cost. More preferred are lime milk and slaked lime. By raising the pH, all or part of impurities contained in the raw material hydrochloric acid or calcium source is precipitated as a hardly soluble substance. The feature of the present invention is that the average primary particle diameter of the calcium salt precipitated in step 2 is 1 to 10 μm, so that the solid-liquid separation is easy even if the particles of the hardly soluble substance precipitated here are fine. .
工程４では、工程３で得られたスラリーを固液分離し、当該スラリー中の固形分を分離除去する。固液分離の方法は特に限定しない。具体的には、加圧や減圧濾過、遠心分離や遠心沈降（デカンター）、液体サイクロンやセトラー等の沈降濃縮等を例示できる。好ましくは設備費が比較的安価で、生産効率が高く、得られる塩化カルシウム水溶液の清澄度を高くできる加圧や減圧濾過、遠心分離であり、より好ましくは加圧濾過である。 In step 4, the slurry obtained in step 3 is subjected to solid-liquid separation, and the solid content in the slurry is separated and removed. The method for solid-liquid separation is not particularly limited. Specific examples include pressurization, vacuum filtration, centrifugal separation, centrifugal sedimentation (decanter), sedimentation concentration of a hydrocyclone, a settler, and the like. Preferably, the equipment cost is relatively low, the production efficiency is high, and pressurization, vacuum filtration, and centrifugal separation that can increase the clarity of the obtained calcium chloride aqueous solution, and more preferred is pressurization filtration.
このようにして得られた塩化カルシウム水溶液は不純物が除去されており、カルシウム化合物の製造原料や排水中のフッ素除去剤、道路の凍結防止剤や冷凍機用ブライン、そして固体状塩化カルシウム粒子の製造原料等として用いることができる。 Impurities have been removed from the calcium chloride aqueous solution thus obtained, and raw materials for calcium compounds, fluorine removing agents in waste water, road freeze inhibitors and brine for refrigerators, and solid calcium chloride particles are produced. It can be used as a raw material.
以下、本発明を実施例及び比較例により具体的に説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to these Examples.
なお、本発明における金属成分の分析は、酸にて溶解後、誘導結合プラズマ発光分光装置（ＩＣＰ−ＡＥＳ）を用い、絶対検量線法にて定量した。ＳＳ（懸濁物質）濃度は、スラリーを捕捉粒子径１μｍの親水性ＰＴＦＥフィルターにて濾過をし、固形分を１１０℃で３時間乾燥した後の乾燥重量から計算にて求めた。 In addition, the analysis of the metal component in the present invention was quantified by an absolute calibration curve method using an inductively coupled plasma emission spectrometer (ICP-AES) after being dissolved in an acid. The SS (suspended substance) concentration was calculated from the dry weight after the slurry was filtered through a hydrophilic PTFE filter having a trapped particle diameter of 1 μm and the solid content was dried at 110 ° C. for 3 hours.
工程２で析出したカルシウムの塩の平均一次粒子径は、走査型電子顕微鏡（日本電子株式会社製、型式：ＪＭ−６０００）を使用し、１０，０００倍で観測した一次粒子を不作為に５０個選んで粒子径を測定し、平均の一次粒子径を求めた。 The average primary particle diameter of the calcium salt precipitated in step 2 was 50 random particles observed at 10,000 times using a scanning electron microscope (manufactured by JEOL Ltd., model: JM-6000). The particle diameter was selected and measured, and the average primary particle diameter was determined.
実施例１
［工程１］内径２０ｃｍ、充填高さ１００ｃｍ、内容積３１．４Ｌの固定床反応槽に、石灰石を６２．０ｋｇ充填した。
Example 1
[Step 1] A fixed bed reaction vessel having an inner diameter of 20 cm, a filling height of 100 cm, and an internal volume of 31.4 L was filled with 62.0 kg of limestone.
尚、石灰石中の炭酸カルシウムの濃度は９４．５ｗｔ％で、不純物としてＭｇが４，１００ｗｔｐｐｍ、Ｐが１，１００ｗｔｐｐｍ、Ｆが２４０ｗｔｐｐｍ、Ｆｅが１５０ｗｔｐｐｍ含まれ、残りの主成分は水であった。 The concentration of calcium carbonate in the limestone was 94.5 wt%, Mg contained 4,100 wtppm, P contained 1,100 wtppm, F contained 240 wtppm, Fe contained 150 wtppm, and the remaining main component was water.
そして、塩素と水素から合成した濃度３６ｗｔ％の塩酸を固定床の下部から２０．３ｋｇ／ｈｒで連続的に供給し、生成した塩化カルシウムのスラリーを固定床の下から７５ｃｍの位置にあるオーバーフロー口から連続的に流出させた。又、３６ｗｔ％塩酸中には不純物としてＦｅが３ｗｔｐｐｍ含まれていた。この固定床では石灰石が消費されるため、上部から石灰石を１５分に１回投入し、充填高さ１００ｃｍを維持するようにした。連続運転５時間を経過した時点で、オーバーフローしたスラリーの一部をサンプリングし、組成を分析したところ、塩化カルシウム濃度４２．０ｗｔ％、塩酸濃度０．８ｗｔ％、ＳＳ濃度０．１５ｗｔ％で、ＳＳは黒色で、ＳＳの主成分は斜緑泥石であった。この塩化カルシウム水溶液を１４０Ｌの樹脂製容器に約１２０Ｌ受け、工程２以降の原料とした。
［工程２及び工程３］工程２と工程３はいずれもオーバーフロー口を有した塩ビ製の攪拌槽であり、内径２４ｃｍ、高さ２２ｃｍ、内容積１０Ｌで、これをシリーズとした。工程２の撹拌槽へは、工程１で得られた塩化カルシウム水溶液を２３ｋｇ／ｈｒ、アルカリ剤として７ｗｔ％の炭酸ナトリウム水溶液を３ｋｇ／ｈｒで連続的に供給した。工程２のオーバーフロー口でのｐＨは３．４で、この工程では平均一次粒子径が４μｍの結晶性の炭酸カルシウム粒子と微細なフッ素化アパタイト粒子が析出した。
Then, 36 wt% hydrochloric acid synthesized from chlorine and hydrogen is continuously supplied from the lower part of the fixed bed at 20.3 kg / hr, and the generated calcium chloride slurry is supplied to the overflow port located 75 cm from the lower part of the fixed bed. Spilled continuously from. Further, 36 wt% hydrochloric acid contained 3 wt ppm of Fe as an impurity. Since limestone is consumed in this fixed bed, limestone was introduced from the top once every 15 minutes to maintain a filling height of 100 cm. When 5 hours of continuous operation passed, a part of the overflowed slurry was sampled and the composition was analyzed. As a result, when the calcium chloride concentration was 42.0 wt%, the hydrochloric acid concentration was 0.8 wt%, the SS concentration was 0.15 wt%, Was black, and the main component of SS was oblique chlorite. About 120 L of this calcium chloride aqueous solution was received in a 140 L resin container, and used as a raw material for step 2 and subsequent steps.
[Steps 2 and 3] Steps 2 and 3 are both vinyl chloride stirring tanks having an overflow port, and have an inner diameter of 24 cm, a height of 22 cm, and an internal volume of 10 L. To the stirring tank of Step 2, the calcium chloride aqueous solution obtained in Step 1 was continuously supplied at 23 kg / hr, and a 7 wt% sodium carbonate aqueous solution as an alkaline agent was continuously supplied at 3 kg / hr. The pH at the overflow port in Step 2 was 3.4. In this step, crystalline calcium carbonate particles having an average primary particle size of 4 μm and fine fluorinated apatite particles were precipitated.
工程３の反応槽には、工程２でオーバーフローしたスラリー全量と２０ｗｔ％石灰乳スラリーを連続的に供給し、ｐＨを９．０〜９．２となるようにコントロールした。工程３では、微細な水酸化マグネシウム粒子の析出が認められた。工程３の撹拌槽からオーバーフローしたスラリーのＳＳ濃度１．０ｗｔ％、塩化カルシウム濃度３５．５ｗｔ％、ｐＨ９．１であった。ここで得られたスラリー７０Ｌを１００Ｌ樹脂製容器に貯蔵し、工程４の原料とした。
［工程４］工程３で得られたスラリーを、ＩＨＩ社製フンダバックフィルターにて濾過速度を測定した。濾過面積０．０６ｍ２、濾過圧力３ｋｇ／ｃｍ２、ポリプロピレン製濾布を用いたところ、濾液は１時間で１３．８ｋｇを得、濾過性が良かった。この濾液の塩化カルシウム水溶液には、不純物のＭｇ、Ｐ、Ｆ、Ｆｅがいずれも１０ｗｔｐｐｍ以下と少なく、石膏の原料として利用可能とわかった。
The total amount of the slurry overflowed in step 2 and the 20 wt% lime milk slurry were continuously supplied to the reaction tank of step 3, and the pH was controlled to be 9.0 to 9.2. In step 3, precipitation of fine magnesium hydroxide particles was observed. The SS concentration of the slurry overflowed from the stirring tank in Step 3 was 1.0 wt%, the calcium chloride concentration was 35.5 wt%, and the pH was 9.1. 70 L of the slurry obtained here was stored in a 100 L resin container and used as the raw material of Step 4.
[Step 4] The filtration rate of the slurry obtained in Step 3 was measured with a Fundac filter manufactured by IHI. When a filtration area of 0.06 m 2 , a filtration pressure of 3 kg / cm 2 and a polypropylene filter cloth were used, 13.8 kg of filtrate was obtained in 1 hour, and the filterability was good. The calcium chloride aqueous solution of this filtrate contained impurities Mg, P, F and Fe as low as 10 wtppm or less, and was found to be usable as a raw material for gypsum.
実施例２
［工程１］実施例１と同じ塩化カルシウム水溶液を用い、工程２以降の原料とした。
［工程２及び工程３］使用する炭酸水素ナトリウム水溶液の濃度を８ｗｔ％に、工程２のオーバーフローのｐＨを３．７にした以外は実施例１と同じ操作を行った。
Example 2
[Step 1] The same calcium chloride aqueous solution as in Example 1 was used as the raw material for Step 2 and subsequent steps.
[Steps 2 and 3] The same operation as in Example 1 was performed except that the concentration of the aqueous sodium hydrogen carbonate solution used was 8 wt% and the overflow pH in Step 2 was 3.7.
工程３の撹拌槽からオーバーフローしたスラリーのＳＳ濃度１．２ｗｔ％、塩化カルシウム濃度３５．４ｗｔ％、ｐＨ９．０であった。ここで得られたスラリー６０Ｌを１００Ｌ樹脂製容器に貯蔵し、工程４の原料とした。
［工程４］実施例１と同じ濾過装置にて工程３で得られたスラリーの濾過速度を測定した。その結果、濾液は１時間で１５．６ｋｇを得ることができ、固液分離が容易で、この濾液は、不純物のＭｇ、Ｐ、Ｆ、Ｆｅがいずれも１０ｗｔｐｐｍ以下と少なく、石膏の原料として利用可能とわかった。
The SS concentration of the slurry overflowed from the stirring tank in Step 3 was 1.2 wt%, the calcium chloride concentration was 35.4 wt%, and the pH was 9.0. 60 L of the slurry obtained here was stored in a 100 L resin container and used as the raw material of Step 4.
[Step 4] Using the same filtration apparatus as in Example 1, the filtration rate of the slurry obtained in Step 3 was measured. As a result, 15.6 kg of the filtrate can be obtained in one hour, and solid-liquid separation is easy, and this filtrate is low in impurities, such as Mg, P, F, and Fe, and is used as a raw material for gypsum. I found it possible.
比較例１
［工程１］実施例１と同じ塩化カルシウム水溶液を用い、工程２以降の原料とした。
［工程２及び工程３］実施例１と同じ装置にて、工程１で得られた塩化カルシウムのスラリーを２３ｋｇ／ｈｒに、７ｗｔ％の炭酸ナトリウム水溶液の代わりに、２０ｗｔ％石灰乳スラリーを０．０９ｋｇ／ｈｒで連続的に供給した。工程２のオーバーフロー口でのｐＨは３．２で、この工程では微細なフッ素化アパタイト粒子の析出のみ確認でき、結晶性の炭酸カルシウム粒子は全く観測できなかった。以降の工程は実施例１と同じ操作を行った。
Comparative Example 1
[Step 1] The same calcium chloride aqueous solution as in Example 1 was used as the raw material for Step 2 and subsequent steps.
[Step 2 and Step 3] In the same apparatus as in Example 1, the calcium chloride slurry obtained in Step 1 was replaced with 23 kg / hr, and 20 wt% lime milk slurry was replaced with 0. It was continuously supplied at 09 kg / hr. The pH at the overflow port in step 2 was 3.2. In this step, only the precipitation of fine fluorinated apatite particles could be confirmed, and crystalline calcium carbonate particles could not be observed at all. The subsequent steps were the same as in Example 1.
工程３の撹拌槽からオーバーフローしたスラリーのＳＳ濃度０．８ｗｔ％、塩化カルシウム濃度３６．４ｗｔ％、ｐＨ９．１であった。ここで得られたスラリーのうち６５Ｌを１００Ｌ樹脂製容器に貯蔵し、工程４の原料とした。
［工程４］実施例１と同じ濾過装置にて工程３で得られたスラリーの濾過速度を測定した。その結果、１時間での濾液量は３．２ｋｇと非常に少なく、濾過速度が小さく、固液分離が困難であることが判った。但し、この濾液は、不純物のＭｇ、Ｐ、Ｆ、Ｆｅがいずれも１０ｗｔｐｐｍ以下と少なく、石膏の原料として利用可能とわかった。
The SS concentration of the slurry overflowed from the stirring tank in Step 3 was 0.8 wt%, the calcium chloride concentration was 36.4 wt%, and the pH was 9.1. 65 L of the slurry obtained here was stored in a 100 L resin container and used as the raw material of Step 4.
[Step 4] Using the same filtration apparatus as in Example 1, the filtration rate of the slurry obtained in Step 3 was measured. As a result, it was found that the amount of filtrate per hour was as very low as 3.2 kg, the filtration rate was low, and solid-liquid separation was difficult. However, this filtrate was found to be usable as a raw material for gypsum because impurities Mg, P, F, and Fe were all low at 10 wtppm or less.
本発明は、不純物を含む塩酸及び／又はカルシウム源から塩化カルシウム水溶液を製造する方法であって、カルシウム塩を析出させることで、微細な不純物結晶を析出させても固液分離が容易、且つ、不純物を効率的に除去でき、設備をコンパクトにできる。 The present invention is a method for producing a calcium chloride aqueous solution from hydrochloric acid and / or calcium source containing impurities, and by precipitating calcium salt, solid-liquid separation is easy even if fine impurity crystals are precipitated, and Impurities can be removed efficiently and the equipment can be made compact.
以上のことから、本発明は、塩化カルシウム水溶液の製造設備に適用できる可能性を有する。 From the above, the present invention has a possibility of being applicable to a production facility for an aqueous calcium chloride solution.
Claims (7)
工程１：塩酸とカルシウム源とを反応させる工程
工程２：工程１で得られた未反応塩酸を含む塩化カルシウム水溶液に薬剤を添加し、平均一次粒子径１〜１０μｍのカルシウム塩を析出させる工程
工程３：工程２で得られたスラリーにアルカリ剤を添加し、そのｐＨを６〜１２の範囲とする工程
工程４：工程３で得られたスラリーを固液分離し、当該スラリー中の固形分を分離除去する工程 The manufacturing method of the calcium chloride aqueous solution including the following processes.
Step 1: A step of reacting hydrochloric acid with a calcium source Step 2: A step of adding a chemical to the calcium chloride aqueous solution containing unreacted hydrochloric acid obtained in Step 1 to precipitate a calcium salt having an average primary particle diameter of 1 to 10 μm. 3: A step of adding an alkaline agent to the slurry obtained in step 2 to adjust the pH to a range of 6 to 12 Step 4: Solid-liquid separation of the slurry obtained in step 3 and removing the solid content in the slurry Separation and removal process
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