JP2019189471A - Manufacturing method of food additives and antibacterial/disinfecting/sterilizing materials using calcium components in hard water - Google Patents
Manufacturing method of food additives and antibacterial/disinfecting/sterilizing materials using calcium components in hard water Download PDFInfo
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本発明は、硬水である地下水や河川水に含まれるカルシウム成分を凝集（晶析）採取・除去するスケール対策に関する技術であり、工業用水或いは飲料用水の配管などの機器設備の延命化を図るものである。同時に本発明は、従来、産業廃棄物として廃棄されていた採取除去後のカルシウム成分を加工し、これを食品添加材や抗菌材等の有効資源に再利用する資源のリサイクル技術に関するものでもある。 [Technical Field] The present invention is a technique related to scale measures for collecting and removing calcium components contained in groundwater or river water, which is hard water, and extends the life of equipment such as piping for industrial water or drinking water. It is. At the same time, the present invention relates to a resource recycling technique for processing a calcium component after being collected and removed, which has been conventionally discarded as industrial waste, and reusing it as an effective resource such as a food additive or an antibacterial material.
工業用水などを大量に使用する工場や事業所等においては、製品製造コストの低減を図る趣旨から、一般の上水道ではなく地下水や河川水を利用することが多い。しかしながら、地域によっては、地下水や河川水がカルシウム成分を多量に含む硬水である場合があり、通常の浄水処理では除去できないカルシウム成分が、施設内の配管や機器設備等にスケールとして付着し施設設備の維持管理に問題を来すことが多い。 In factories and business establishments that use a large amount of industrial water and the like, groundwater and river water are often used instead of general waterworks in order to reduce product manufacturing costs. However, depending on the area, groundwater and river water may be hard water containing a large amount of calcium components, and calcium components that cannot be removed by normal water purification treatment adhere to the piping and equipment in the facility as scales. Often causes problems in maintenance.
これらの配管や機器設備に付着したスケールは、非常に硬くかつ水に溶けにくい物質であり、工具などによる物理的な除去は極めて困難である。特に、カルシウム成分は水中の二酸化炭素と結びつき炭酸カルシウムとなって、難溶性の針状結晶であるアラゴナイトを析出し、例えば配管内壁などにおいて係る結晶が析出・成長するため強固なスケールが増大してしまう。 The scales attached to these pipes and equipment are extremely hard and hardly soluble in water, and physical removal with a tool or the like is extremely difficult. In particular, the calcium component is combined with carbon dioxide in water to form calcium carbonate, which precipitates aragonite, which is a sparingly soluble acicular crystal. End up.
このため、硬水使用量の多い事業所などでは、硬水中のカルシウム除去方法として効率の良い凝集（晶析）法による対策を講じている。因みに、凝集（晶析）法とは、カルシウムの結合・吸着・回収がスムーズにできるように、予め、硬水に極微細核（ペレット）を投入した後、これにアルカリ材を加えペーハー調整を行い、硬水中のカルシウム成分を不溶性炭酸カルシウム生成粒として、硬水から分離・回収する方法を言う。 For this reason, in business establishments where the amount of hard water used is large, measures are taken by an efficient coagulation (crystallization) method as a method for removing calcium in hard water. By the way, the agglomeration (crystallization) method is to adjust the pH by adding ultra-fine nuclei (pellets) to hard water in advance, and then adding an alkali material to it so that calcium can be bound, adsorbed and recovered smoothly. This refers to a method of separating and recovering calcium components in hard water as insoluble calcium carbonate-generated grains from hard water.
そして、分離・回収された後の不溶性炭酸カルシウム生成粒は、そのままでは価値が見出せないため、単なる産業廃棄物として廃棄処分されているのが現状である。それ故、係る不溶性炭酸カルシウム生成粒を有効資源として再利用することが可能であれば、産業廃棄物の削減にも繋がり、いわゆるエコロジーな社会経済の実現に貢献することできる。 And since the insoluble calcium carbonate production | generation grain after isolate | separating and collect | recovering cannot find value as it is, it is the present condition that it is discarded as mere industrial waste. Therefore, if it is possible to reuse such insoluble calcium carbonate particles as an effective resource, it will lead to reduction of industrial waste and contribute to the realization of so-called ecological social economy.
ところで、近年、天然のカルシウム素材から水酸化カルシウムを生成し、これを食品添加材や抗菌材として用いる方法が広く社会から注目されるようになった。水酸化カルシウムは、その強いアルカリ性から優れた抗菌・除菌・殺菌効果を有しており、さらに、天然素材由来のものであれば食品に対する安全性などが担保されているためである。 By the way, in recent years, a method of generating calcium hydroxide from a natural calcium material and using it as a food additive or an antibacterial material has been widely attracted by society. This is because calcium hydroxide has excellent antibacterial, sterilizing and bactericidal effects due to its strong alkalinity, and further, safety from foods is ensured if it is derived from natural materials.
これらの天然素材由来のカルシウムを原料とした水酸化カルシウムによる抗菌・除菌・殺菌材などの製造方法としては、例えば、特許文献１や特許文献２に示すような従来技術が開示されている。 As a method for producing antibacterial, sterilizing and disinfecting materials using calcium hydroxide using calcium derived from these natural materials as a raw material, for example, conventional techniques as disclosed in Patent Document 1 and Patent Document 2 are disclosed.
しかしながら、これらの従来技術は製品の原料として、主に天然素材のホタテ貝などの二枚貝の貝殻を用いるものである。そのため、天候などの気象変動によりその供給が左右される場合も多い、また、天然もの、或いは養殖ものを含めて、ホタテ貝などの海産物はその原産地が限られているため、原料入手の地域的な困難性を生ずることも多い。 However, these conventional technologies mainly use bivalve shells such as scallops made of natural materials as raw materials for products. For this reason, the supply of the scallops is often affected by weather fluctuations such as the weather, and seafood such as scallops, including natural or aquaculture, is limited in its origin. Often causes difficulty.
さらに、ホタテ貝などの天然素材では、例えばフジツボなどの付着物も多く、それらの除去がほぼ手作業となり原料コストの高騰を招いていた。また、天然素材のカルシウムには不純物も多く含まれており、これらを除去するため焼成温度を高めに、かつ焼成時間を長く設定する必要が生じ、製造時のエネルギーロスの増大と加工コスト上昇の原因ともなっていた。 Furthermore, in natural materials such as scallops, there are many deposits such as barnacles, for example, and removal of them is almost a manual operation, leading to an increase in raw material costs. In addition, calcium, which is a natural material, contains a lot of impurities. To remove these, it is necessary to increase the firing temperature and set the firing time longer, resulting in increased energy loss during production and increased processing costs. It was also a cause.
本発明は、このような従来からの課題を解決することを目的とするものであって、従来は産業廃棄物として廃棄処分されていた、地下水や河川水から分離回収されたカルシウム成分を、食品添加材や抗菌・除菌・殺菌材として再利用できる方法を提供することを目的とする。 The present invention aims to solve such a conventional problem, and the calcium component separated and recovered from groundwater or river water, which has been conventionally disposed as industrial waste, An object is to provide a method that can be reused as an additive, antibacterial, sterilizing, or disinfecting material.
本発明の第一の観点による食品添加用或いは抗菌・除菌・殺菌用の紛体の製造方法は、地下水や河川水等の硬水に結晶核となるカルシウム微細粒子と苛性ソーダとを混合して、純度９５％以上の炭酸カルシウムを摘出する工程と、摘出された炭酸カルシウムを高温焼成し、これを水和反応させて水酸化カルシウムを生成する工程と、生成された水酸化カルシウムを微細粉砕して純度９５％以上の水酸化カルシウム微細紛体を生成する工程と、を含むことを特徴とする。 The method for producing a powder for food addition or antibacterial / sterilization / sterilization according to the first aspect of the present invention comprises mixing calcium fine particles serving as crystal nuclei and caustic soda into hard water such as groundwater or river water, and purity. A process of extracting 95% or more of calcium carbonate, a process of calcining the extracted calcium carbonate at a high temperature and hydrating it to generate calcium hydroxide, and then purifying the generated calcium hydroxide by fine pulverization And a step of producing 95% or more calcium hydroxide fine powder.
また、本発明の第二の観点による食品添加用或いは抗菌・除菌・殺菌用の紛体の製造方法は、前述の第一の観点において生成された水酸化カルシウムを摂氏８００度〜１，１００度で再び焼成し、脱水可逆反応によって酸化カルシウムに還元する工程と、還元された酸化カルシウムを摂氏５０度〜２００度の雰囲気下で水和反応させ、再度、水酸化カルシウムを生成する工程と、前記工程によって得られた水酸化カルシウムから粒径４５μｍ以下で純度９５％以上の水酸化カルシウム微細紛体を選別する工程と、を含むことを特徴とする。 In addition, the method for producing a powder for food addition or antibacterial / disinfecting / sterilizing powder according to the second aspect of the present invention uses the calcium hydroxide produced in the first aspect described above at 800 to 1,100 degrees Celsius. Calcination again, and reducing to calcium oxide by dehydration reversible reaction; hydration reaction of the reduced calcium oxide in an atmosphere of 50 to 200 degrees Celsius to generate calcium hydroxide again; Screening the calcium hydroxide fine powder having a particle size of 45 μm or less and a purity of 95% or more from the calcium hydroxide obtained by the process.
また、本発明の第三の観点による抗菌・除菌・殺菌用水溶液の製造方法は、前述の第二の観点による紛体を湿式ボールミル又は湿式ジェットミルを用いて、さらに粒径１μｍ以下に微粉砕する工程と、前記工程で得られた微細粉末に基加水して、水酸化カルシウム濃度が０．１７〜０．５質量％で、そのペーハーが１２．５以上の抗菌・除菌・殺菌特性を備えた水酸化カルシウム水溶液を生成する工程と、を含むことを特徴とする。 The method for producing an aqueous solution for antibacterial, sterilization and sterilization according to the third aspect of the present invention further comprises finely pulverizing the powder according to the second aspect to a particle size of 1 μm or less using a wet ball mill or a wet jet mill. To the fine powder obtained in the previous step, the calcium hydroxide concentration is 0.17 to 0.5% by mass, and the pH is 12.5 or more antibacterial / sterilizing / bactericidal properties And a step of generating an aqueous calcium hydroxide solution provided.
本発明によれば、地下水などの硬水対策処理で生成される炭酸カルシウムを凝集（晶析・析出）・回収した砂状石灰粒を基に、これを焼成、水和、粉砕することによりカルシウム純度９５．０％以上の紛体に加工できる。係る生成品は、食品添加物の規格基準に合致した水酸化カルシウム紛体であり、従来、産業廃棄物として単に捨てられていた回収砂状石灰粒を、食品添加材や抗菌・除菌・殺菌材等の高付加価値製品として再び利用することができる。 According to the present invention, calcium purity is obtained by calcining, hydrating, and pulverizing calcium carbonate produced by agglomeration (crystallization / precipitation) / recovery of calcium carbonate generated by a countermeasure against hard water such as groundwater. It can be processed into a powder of 95.0% or more. Such products are calcium hydroxide powder that meets the standards for food additives, and the collected sandy lime particles that have been simply discarded as industrial waste are used as food additives, antibacterial, sanitizing, and disinfecting materials. It can be used again as a high value-added product.
本発明の実施例を示す前に、先ず本発明全体の概要を説明する。なお、本発明による製造方法の処理工程の概要を添付図面の第１図に示す。 Before showing an embodiment of the present invention, an overview of the present invention will be described first. An outline of the processing steps of the manufacturing method according to the present invention is shown in FIG. 1 of the accompanying drawings.
水質の硬度に関する水道水質基準によれば、水１リットル中に含まれる炭酸カルシウムの量が３００ｍｇ以下であることが規定されている。但し、おいしい水としての管理目標硬度は、一般に１０〜１００ｍｇと言われており、そして、硬水の硬度低減処理（以下、単に「硬水処理」と言う。）は、通常の浄水処理である凝集沈殿法や急速濾過法などの方法によっては解決できない。 According to the tap water quality standard regarding the hardness of water quality, it is specified that the amount of calcium carbonate contained in 1 liter of water is 300 mg or less. However, the management target hardness as delicious water is generally said to be 10 to 100 mg, and the hardness reduction treatment of hard water (hereinafter simply referred to as “hard water treatment”) is a coagulation precipitation which is a normal water purification treatment. It cannot be solved by methods such as the rapid filtration method.
そこで、大量の工業用水などの硬水処理を行うためには、独特の凝集（晶析）法を採用することが最も効率が良い。因みに、当該方法を用いれば１日に５，０００トン以上の硬水を処理することも可能である。 Therefore, in order to perform a hard water treatment such as a large amount of industrial water, it is most efficient to employ a unique aggregation (crystallization) method. Incidentally, if this method is used, 5,000 tons or more of hard water can be treated per day.
凝集（晶析）法は、添付図面の図２に示すような方法で行われる。先ず、硬水を導入した流動床反応器内に予めカルシウムの極微細核（ペレット）を添加し流動させ、これに苛性ソーダを加えて全体のペーハーを８〜９に上げる。これによって、ペレットに硬水中の不溶性炭酸カルシウムが付着・成長し、粒径０．１〜０．９ｍｍ程度のランダムな粒状となり、スケールの原因となる硬水中のカルシウム成分を回収する事ができる。 The aggregation (crystallization) method is performed by a method as shown in FIG. 2 of the accompanying drawings. First, calcium fine nuclei (pellets) are added and fluidized beforehand in a fluidized bed reactor into which hard water has been introduced, and caustic soda is added thereto to raise the overall pH to 8-9. As a result, insoluble calcium carbonate in hard water adheres to and grows on the pellets, forming random particles with a particle size of about 0.1 to 0.9 mm, and the calcium component in hard water that causes scale can be recovered.
因みに、係る処理工程の化学反応式は次の通りである。
Ｃａ(ＨＣＯ３)２ ＋ ＮａＯＨ ＝ ＣａＣＯ３ ＋ ＮａＨＣＯ３ ＋ Ｈ２Ｏ
炭酸水素カルシウム 苛性ソーダ 炭酸カルシウム 炭酸水素ナトリウム 水
Incidentally, the chemical reaction formula of the processing step is as follows.
Ca (HCO 3 ) 2 + NaOH = CaCO 3 + NaHCO 3 + H 2 O
Calcium bicarbonate Caustic soda Calcium carbonate Sodium bicarbonate Water
本発明の第１ステップとして、先ず回収された炭酸カルシウムから工業用石灰製造の場合と同様に、高温焼成された生石灰を製造する。通常、石灰の脱炭酸温度は摂氏６００度なので、摂氏７００度以下では良質な生石灰を製造することは難しい。一方、高温度での焼成は、例えば摂氏１，３００度などの記載も散見されるが、装置・設備の構成やエネルギー消費ロス或いは作業所要時間等を勘案すれば、摂氏８００〜１，１００度の範囲とすることが好ましい。因みに、係る事実は各種文献の記載からも確認することができる。 As the first step of the present invention, first, quick calcined calcined lime is produced from the recovered calcium carbonate as in the case of industrial lime production. Usually, since the decarboxylation temperature of lime is 600 degrees Celsius, it is difficult to produce good quality quick lime at 700 degrees Celsius or less. On the other hand, the firing at a high temperature is sometimes described as 1,300 degrees Celsius, for example, but considering the configuration of equipment / equipment, energy consumption loss, working time, etc., 800-1100 degrees Celsius It is preferable to set it as the range. Incidentally, such facts can also be confirmed from descriptions in various documents.
炭酸カルシウムを焼成した酸化カルシウム（生石灰）は、水と反応すると激しく発熱して危険を伴う。そのため、生石灰の含有量が８０％を超える化学物質を５００ｋｇ以上取り扱う場合は、通常、所轄消防署への届け出が義務付けられている。本発明ではこのようなリスクを回避すべく、第２ステップとして、予め工場で焼成した生石灰に加水し、水和反応により水酸化カルシウム（消石灰）に加工して製品の保存性、可搬性を担保する。 Calcium oxide (quick lime) obtained by baking calcium carbonate reacts with water and generates heat violently. Therefore, when handling 500 kg or more of a chemical substance with a quicklime content exceeding 80%, it is usually required to report to the local fire department. In the present invention, in order to avoid such a risk, as a second step, water is added to quick lime calcined in the factory in advance and processed into calcium hydroxide (slaked lime) by a hydration reaction to ensure the storage stability and portability of the product. To do.
水和処理は、散水或いは噴霧により行う事が好ましい。本発明の水和条件としては、摂氏５０度以上の雰囲気下で水和反応を進め、水蒸気の結露による消石灰の品質低下を防止している。なお、水和処理の雰囲気が摂氏４００度を超えると、消石灰の脱水可逆反応が進行する懸念があるので、概ね摂氏５０〜２００度程度の雰囲気中で作業を行うことが好ましい。 The hydration treatment is preferably performed by watering or spraying. As the hydration conditions of the present invention, the hydration reaction is carried out in an atmosphere of 50 degrees Celsius or higher to prevent the quality of slaked lime from being deteriorated due to condensation of water vapor. In addition, since there exists a possibility that the dehydration reversible reaction of slaked lime may advance when the atmosphere of a hydration process exceeds 400 degreeC, it is preferable to work in the atmosphere of about 50 to 200 degreeC.
以上の工程によって生成された水酸化カルシウム（消石灰）は、そのままでも十分に産業上の利用価値を有するものであるが、これを、さらに高付加価値の食品添加材や抗菌・除菌・殺菌材として使用するためには、水酸化カルシウム紛体の紛体粒径の粒度分布管理が重要なファクターとなる。 Calcium hydroxide (slaked lime) produced by the above process has sufficient industrial utility value as it is, but it can be used as a food additive or antibacterial / disinfectant / disinfectant with higher added value. Therefore, the particle size distribution management of the particle size of the calcium hydroxide powder is an important factor.
そのため、製造された水酸化カルシウムの粉砕をピンミルやジェットミル、或いはロール式等の乾式粉砕機器を使用する他、湿式ボールミル、湿式ジェットミルなどの粉砕機器を用いて、さらに微細化することによって製品用途の拡大を図ることができる。因みに、粒径の粒度管理は篩分級や、各種のスクリーン或いはフィルターを用いて行うものとする。 Therefore, in addition to using a dry mill such as a pin mill, jet mill, or roll type, the manufactured calcium hydroxide is further refined using a mill such as a wet ball mill or a wet jet mill. Applications can be expanded. Incidentally, the particle size control is performed using sieve classification, various screens or filters.
また、製品紛体の微細化は、次の第３ステップの工程を経ることで達成することも可能である。すなわち、以上の過程で水和反応させた消石灰を、さらに摂氏８００〜１，１００度の温度範囲で焼成し、再度、脱水反応を起こさせて生石灰に還元する。そして、再び摂氏５０〜２００度の雰囲気下に置き水和反応起こさせることによって、粒径の粒度が４５μｍ以下の水酸化カルシウムを得ることができる。 Further, the refinement of the product powder can be achieved through the following third step. That is, the slaked lime that has been hydrated in the above process is further baked in a temperature range of 800 to 1100 degrees Celsius, and again dehydrated to be reduced to quick lime. Then, by placing again in an atmosphere of 50 to 200 degrees Celsius and causing a hydration reaction, calcium hydroxide having a particle size of 45 μm or less can be obtained.
（実施例）
本発明の具体的な実施例について以下に説明を行う。本実施例に紹介する事業所では工業用水を得るために、１日に６，０００〜７，０００ｍ３の硬水処理を行っており、その原水は地下から汲み上げた井戸水（地下水）である。
(Example)
Specific examples of the present invention will be described below. In order to obtain industrial water, the establishment introduced in this example performs hard water treatment of 6,000 to 7,000 m 3 per day, and the raw water is well water (ground water) pumped from the ground.
原水の平均硬度は、原水１リットル中に約３２０ｍｇの炭酸カルシウムが含まれており、同事業所ではこれを８０ｍｇ／リットル以下まで低下させて飲料用ならびに食品加工用に使用している。なお、凝集（晶析・析出）による炭酸カルシウムの産出量は、年間で約１，４００〜１，６００トンに及んでいる。 The average hardness of raw water contains about 320 mg of calcium carbonate in 1 liter of raw water, and this is reduced to 80 mg / liter or less and used for beverages and food processing. The amount of calcium carbonate produced by agglomeration (crystallization / precipitation) is about 1,400 to 1,600 tons per year.
前述した図２の方法で採取された凝集（晶析・析出）カルシウム成分は、炭酸カルシウム９５％以上であり、その他の成分としては、鉄、マンガンなどのミネラル分が含まれている。また、その外観は白色であり、密度は２．７ｇ／Ｃｍ３、含水率は３〜４％である。また、回収されたカルシウム粒径の粒度分布は、０．１ｍｍ以下２％、２．０ｍｍ以下７４％、５．０ｍｍ以下２３％、９．０ｍｍ以下１％と成っていた。 The agglomerated (crystallized / precipitated) calcium component collected by the method shown in FIG. 2 is 95% or more of calcium carbonate, and other components include minerals such as iron and manganese. Moreover, the external appearance is white, a density is 2.7 g / Cm < 3 >, and a moisture content is 3 to 4%. The particle size distribution of the recovered calcium particle size was 0.1 mm or less 2%, 2.0 mm or less 74%, 5.0 mm or less 23%, 9.0 mm or less 1%.
また、同事業所内の配管や機器設備にはスケールの付着は確認できず、他の機器設備と同様に定期メンテナンスのみで対応が可能であり、特段のメンテナンスは必要としない状況が確認された。なお、従来は析出・回収された炭酸カルシウムは、土木工事用の骨材などに、無料や砂礫以下の価格で引き渡され処分されていたとの事である。 In addition, it was not possible to confirm the adhesion of scales to the piping and equipment in the office, and it was possible to deal with only regular maintenance like other equipment, and it was confirmed that no special maintenance was required. In the past, the precipitated and recovered calcium carbonate was delivered and disposed of free of charge or below the gravel on aggregates for civil engineering work.
本実施例では、先ず、凝集（晶析・析出）回収された炭酸カルシウムを摂氏８００〜１，０００度、好ましくは摂氏９００〜１，０００度の範囲で焼成して脱炭酸処理を行った。また、焼成時間は１時間以上４時間未満、好ましくは２〜４時間の範囲で焼成を行った。
因みに、焼成前の重量１００ｇの炭酸カルシウムを、２時間焼成後に秤量すると４９ｇに減量した。なお、２時間の焼成で原料の重量は、ほぼ平衡値に到り係る重量減少を以って焼成処理の完了と判定した。
In this example, first, calcium carbonate collected in an aggregate (crystallization / precipitation) was calcined in a range of 800 to 1,000 degrees Celsius, preferably 900 to 1,000 degrees Celsius, and then decarboxylated. The firing time was 1 hour or more and less than 4 hours, preferably 2 to 4 hours.
Incidentally, when calcium carbonate having a weight of 100 g before firing was weighed after firing for 2 hours, it was reduced to 49 g. In addition, it was determined that the firing process was completed when the weight of the raw material reached the equilibrium value after the firing for 2 hours, and the weight decreased.
次に水和処理は、焼成されたカルシウムに対して３５〜５０質量％、好ましくは４０〜４５質量％の水を万遍なく散布して行った。さらに、二次的に２〜５質量％の水を、全体に噴霧して水和処理にムラが発生することを防止した。なお、水和処理の過程において、水の散布と噴霧を行う容器内は、全体の温度が摂氏１００〜１２０度となるように面ヒーターで加温し、水和処理の安定化と結露の防止を図った。 Next, the hydration treatment was performed by uniformly spraying 35 to 50% by mass, preferably 40 to 45% by mass of water with respect to the calcined calcium. Furthermore, 2 to 5% by mass of water was secondarily sprayed to prevent unevenness in the hydration treatment. In the hydration process, the inside of the container where water is sprayed and sprayed is heated with a surface heater so that the overall temperature is 100 to 120 degrees Celsius, stabilizing the hydration process and preventing condensation. I planned.
水和処理の終了後、室温に低下した水酸化カルシウムに加水して、０．２質量％の水酸化カルシウム水溶液を作成し同溶液のペーハーを計測した。その結果、測定値はペーハー１２．６〜１２．８を示し、当該計測を１０回の取得サンプルについて行ったが、係る測定値は安定して再現することができた。なお、ペーハー計測には（株）堀場製作所製の「水質分析計Ｆ−７２」を用いている。 After completion of the hydration treatment, water was added to calcium hydroxide lowered to room temperature to prepare a 0.2% by mass calcium hydroxide aqueous solution, and the pH of the solution was measured. As a result, the measured value showed a pH of 12.6 to 12.8, and the measurement was performed for 10 acquired samples. However, the measured value could be stably reproduced. For the pH measurement, “Water Quality Analyzer F-72” manufactured by HORIBA, Ltd. is used.
さらに、上記の水酸化カルシウムの紛体に関し、食品、添加物等の規格基準の適合可否確認を行うべく、当該基準の粉末の粒度４５μｍ篩残分１％以下という項目について試験を行った。すなわち、水和・冷却した後の水酸化カルシウムをピンミルで１１，０００ｒｐｍで２回に亘り粉砕処理を行い、生成粉末の粒度を測定したところ粒度４５μｍ篩残分１％以下という基準に適合しているという結果が確認された。 Furthermore, with respect to the above powder of calcium hydroxide, in order to confirm whether or not the standards of foods, additives, and the like can be met, the test was performed on the item of powder having a particle size of 45 μm sieve residue of 1% or less. In other words, the calcium hydroxide after hydration and cooling was pulverized twice at 11,000 rpm with a pin mill, and the particle size of the resulting powder was measured. The result was confirmed.
また、食品、添加物等の規格基準に関するその他の項目についても検査を行い、全ての項目について規格基準に適合していることが確認された。なお、係る検査は（財）日本食品分析センターにて実施され、添付図面の図３にその試験成績書を示す。因みに、同成績書において結果欄に「適」と記載されている事が適合性を確認された事実を示している。 In addition, other items related to standard standards such as food and additives were also inspected, and it was confirmed that all items conformed to standard standards. This inspection is conducted at the Japan Food Analysis Center, and the test report is shown in FIG. 3 of the accompanying drawings. Incidentally, the fact that “appropriate” is described in the result column in the same report indicates the fact that the conformity has been confirmed.
前述したように、水酸化カルシウムは強いアルカリ性（ペーハー１２以上）を示し、強力な殺菌・消毒効果を有している。このため、畜産分野の消毒用として頻繁に利用されている。例えば、東京都の家畜保健場の広報でも、畜産類の飼育場などにおいての紛体散布、或いは水溶液散布、又は紛体或いは水溶液の畜舎設備などへの塗布が推奨されている。 As described above, calcium hydroxide exhibits strong alkalinity (pH 12 or higher) and has a strong sterilizing / disinfecting effect. For this reason, it is frequently used for disinfection in the field of livestock. For example, in the public relations of a livestock health center in Tokyo, it is recommended to spray powder in livestock breeding farms, spray aqueous solution, or apply powder or aqueous solution to barn facilities.
なお、幅広く殺菌・消毒処理を行うためには、水溶液による噴霧散布がより好ましい。このため、水酸化カルシウム紛体を更に微細化して、散布用噴霧ノズルのつまりを防止することが必要となる。本実施例では、湿式ボールミルで前述の水酸化カルシウム紛体を、さらに１．０μｍ以下に微細化粉砕することで係る目的を達成している。 In addition, in order to perform sterilization / disinfection treatment widely, spraying with an aqueous solution is more preferable. For this reason, it is necessary to further refine the calcium hydroxide powder to prevent the spray nozzles from clogging. In this example, the above-mentioned calcium hydroxide powder is further refined and pulverized to 1.0 μm or less by a wet ball mill to achieve the object.
また、本実施例では、水酸化カルシウムの水溶・分散液を生成する場合の水酸化カルシウム紛体の添加量は若干過飽和気味とした。すなわち、通常の水酸化カルシウム水溶液の飽和溶融密度は０．１７ｇ／１００Ｃｍ３（摂氏２５度）であるが、本実施例では０．２〜０．５ｇ／１００Ｃｍ３（摂氏２５度）に調整している。 In this example, the amount of calcium hydroxide powder added in the case of producing an aqueous solution or dispersion of calcium hydroxide was slightly supersaturated. That is, the saturation melt density of a normal calcium hydroxide aqueous solution is 0.17 g / 100 Cm 3 (25 degrees Celsius), but in this example, it is adjusted to 0.2 to 0.5 g / 100 Cm 3 (25 degrees Celsius). ing.
続いて係る条件に設定した水酸化カルシウム水溶液を用い、大腸菌（Ｏ−１５７）、サルモネラ菌、黄色ブドウ球菌に対する殺菌作用の確認試験を実施した。その結果、各種細菌は、試験開始後３０分で全て殺菌されていること（検出せず）が証明され、その有効性が確認された。 Subsequently, using a calcium hydroxide aqueous solution set to such conditions, a confirmation test of bactericidal action against Escherichia coli (O-157), Salmonella, and Staphylococcus aureus was performed. As a result, it was proved that various bacteria were all sterilized 30 minutes after the start of the test (not detected), and their effectiveness was confirmed.
なお、係る確認試験は（財）日本食品分析センターにて行い、添付図面の図４にその試験成績書を示す。因みに、同試験成績書中の検体名として記載された「レキオパワー」なる名称は、本発明に基づく製造方法によって製造された水酸化カルシウム粉末、及び水溶液の製品名である。 This confirmation test is conducted at the Japan Food Analysis Center, and the test report is shown in FIG. 4 of the accompanying drawings. Incidentally, the name “Requio Power” described as the specimen name in the test report is the product name of calcium hydroxide powder and aqueous solution manufactured by the manufacturing method according to the present invention.
ところで、通常の水酸化カルシウム飽和水溶液は、その容器を室内開放状態で放置すると約１週間経過後に、そのペーハーが８．０以下に低下して殺菌・消毒効果が消失する。しかしながら、本実施例で生成した水酸化カルシウム過飽和水溶液では１週間経過後も、そのペーハーを１２．４〜１２．５に維持しペーハーの大幅な低下を来たすことはなかった。 By the way, the normal calcium hydroxide saturated aqueous solution loses its sterilizing / disinfecting effect when its container is left in an indoor open state after about one week and the pH is lowered to 8.0 or less. However, with the calcium hydroxide supersaturated aqueous solution produced in this example, the pH was maintained at 12.4 to 12.5 even after one week, and the pH was not significantly reduced.
一方、前述の水和反応を起こさせて室温にまで冷却した水酸化カルシウムを、摂氏８００〜１，１００度の範囲で再度焼成し脱水反応させて生石灰に還元する。その後、これを摂氏５０〜２００度の雰囲気下に置き、再び水和反応を起こさせることによって採取された消石灰は、各種の粉砕機器を使用することなく、その粒度が４５μｍでカルシウム純度が９５％以上の水酸化カルシウム粉末となることが確認された。 On the other hand, calcium hydroxide that has been subjected to the above-described hydration reaction and cooled to room temperature is fired again in the range of 800 to 1,100 degrees Celsius for dehydration and reduced to quick lime. After that, the slaked lime collected by placing it in an atmosphere of 50 to 200 degrees Celsius and causing a hydration reaction again has a particle size of 45 μm and a calcium purity of 95% without using various grinding equipment. It was confirmed that the above calcium hydroxide powder was obtained.
このようにして製造した水酸化カルシウムを室温下において加水し、０．２質量％の水酸化カルシウム水溶液を生成したところ、そのペーハー測定値結果は１２．９〜１３．２の値を示した。この測定値は、１０回のサンプル計測を行った場合でも常に安定して再現することができた。 The calcium hydroxide produced in this manner was hydrated at room temperature to produce a 0.2 mass% calcium hydroxide aqueous solution. The pH measurement result showed a value of 12.9 to 13.2. This measured value was always able to be reproduced stably even when 10 sample measurements were performed.
すなわち、本実施例においては、焼成・水和の処理過程を再度繰り返すことによって水酸化カルシウム紛体の粒径がさらに細微になり、係る粉末を用いた水酸化カルシウム水溶液の強アルカリ性が増すことが確認された。 That is, in this example, it was confirmed that the particle size of the calcium hydroxide powder was further refined by repeating the baking and hydration process again, and the strong alkalinity of the calcium hydroxide aqueous solution using the powder increased. It was done.
以上に説明したように、本発明に基づく食品添加材、或いは抗菌・除菌・殺菌材の原材料は、ホタテ貝殻などの天然素材ではなく、地下水などの硬水から分離・回収された炭酸カルシウムを使用している。それ故、原材料に含まれる不純物の割合が少なく純度の高いカルシウム成分を摘出できる。このため、原材料から酸化カルシウムを生成する焼成時間を短縮することが可能であり、酸化カルシウムを水和して生成された水酸化カルシウム粉末の粒径も、抗菌・除菌・殺菌の用途に適したものを容易に得ることができる。 As explained above, the raw material for food additives or antibacterial / sterilizing / sterilizing materials according to the present invention is not natural materials such as scallop shells, but uses calcium carbonate separated and recovered from hard water such as groundwater. is doing. Therefore, it is possible to extract a calcium component having a high purity with a small proportion of impurities contained in the raw material. For this reason, it is possible to shorten the baking time for generating calcium oxide from raw materials, and the particle size of calcium hydroxide powder generated by hydrating calcium oxide is also suitable for antibacterial, sterilization and sterilization applications. Can be easily obtained.
なお、本発明の実施形態は、以上に説明した実施例に限定されるものではなく、例えば、各々の実施例を構成する各部位の形状や配置、或いはその素材などは、本発明の趣旨を逸脱することなく、現実の実施態様に即して適宜変更ができるものであることは言うまでもない。 The embodiments of the present invention are not limited to the examples described above. For example, the shape and arrangement of each part constituting each of the examples, or the material thereof is the gist of the present invention. It goes without saying that changes can be made as appropriate according to actual embodiments without departing.
以上に説明した本発明の構成ならびに方法は、硬水処理の結果発生するカルシウム成分を有効資源として再生する技術の分野においてその利用が可能である。 The configuration and method of the present invention described above can be used in the technical field of regenerating calcium components generated as a result of hard water treatment as effective resources.
Claims (3)
摘出された炭酸カルシウムを高温焼成し、これを水和反応させて水酸化カルシウムを生成する工程と、
生成された水酸化カルシウムを微細粉砕して純度９５％以上の水酸化カルシウム微細紛体を生成する工程と、
を含む食品添加用或いは抗菌・除菌・殺菌用の紛体の製造方法。 A process of extracting calcium carbonate having a purity of 95% or more by mixing calcium fine particles serving as crystal nuclei and caustic soda into hard water such as ground water or river water;
Calcination of the extracted calcium carbonate at a high temperature, hydration reaction of this to produce calcium hydroxide,
Finely pulverizing the produced calcium hydroxide to produce a calcium hydroxide fine powder having a purity of 95% or more;
For the production of powders for food addition or antibacterial / sterilization / sterilization
還元された酸化カルシウムを摂氏５０度〜２００度の雰囲気下で水和反応させ、再度、水酸化カルシウムを生成する工程と、
前記工程によって得られた水酸化カルシウムから粒径４５μｍ以下で純度９５％以上の水酸化カルシウム微細紛体を選別する工程と、
を含む食品添加用或いは抗菌・除菌・殺菌用の紛体の紛体の製造方法。 Calcining the calcium hydroxide according to claim 1 again at 800 to 1100 degrees Celsius and reducing it to calcium oxide by a dehydration reversible reaction;
Hydration reaction of the reduced calcium oxide in an atmosphere of 50 degrees Celsius to 200 degrees Celsius to generate calcium hydroxide again;
Selecting a calcium hydroxide fine powder having a particle size of 45 μm or less and a purity of 95% or more from the calcium hydroxide obtained by the step;
For the production of powders for food additives containing or for antibacterial, sterilization and sterilization.
前記工程で得られた微細粉末に加水して、水酸化カルシウム濃度が０．１７〜０．５質量％で、そのペーハーが１２．５以上の抗菌・除菌・殺菌特性を備えた水酸化カルシウム水溶液を生成する工程と、
を含む抗菌・除菌・殺菌用水溶液の製造方法。
A step of further pulverizing the powder according to claim 2 to a particle size of 1 μm or less using a wet ball mill or a wet jet mill;
Calcium hydroxide with antibacterial, antibacterial and bactericidal properties with a calcium hydroxide concentration of 0.17 to 0.5% by mass and a pH of 12.5 or more by adding water to the fine powder obtained in the above step Producing an aqueous solution;
Of an aqueous solution for antibacterial, sterilization and sterilization containing
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| JP2022136906A (en) * | 2021-03-08 | 2022-09-21 | フィーネ株式会社 | Method for producing calcium hydroxide powder for washing fruits and vegetables and method for washing fruits and vegetables using the calcium hydroxide powder |
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| JPH08109017A (en) * | 1994-10-11 | 1996-04-30 | Tanaka Sekkai Kogyo Kk | Slaked lime and its production |
| JP2001123071A (en) * | 1999-08-19 | 2001-05-08 | Kaisui Kagaku Kenkyusho:Kk | Method for producing calcium hydroxide and resin composition |
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| JPH08109017A (en) * | 1994-10-11 | 1996-04-30 | Tanaka Sekkai Kogyo Kk | Slaked lime and its production |
| JP2001123071A (en) * | 1999-08-19 | 2001-05-08 | Kaisui Kagaku Kenkyusho:Kk | Method for producing calcium hydroxide and resin composition |
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| CN111762941A (en) * | 2020-05-28 | 2020-10-13 | 内蒙古久科康瑞环保科技有限公司 | System and method for treating wastewater by recycling calcium carbonate |
| JP2022136906A (en) * | 2021-03-08 | 2022-09-21 | フィーネ株式会社 | Method for producing calcium hydroxide powder for washing fruits and vegetables and method for washing fruits and vegetables using the calcium hydroxide powder |
| JP7158764B2 (en) | 2021-03-08 | 2022-10-24 | フィーネ株式会社 | Method for producing calcium hydroxide powder for washing fruits and vegetables and method for washing fruits and vegetables using the calcium hydroxide powder |
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