JP6364260B2 - Method for producing magnesium peroxide granules - Google Patents
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本発明は、過酸化物として有用な過酸化マグネシウム粒剤の製造方法に関する。 The present invention relates to a method for producing magnesium peroxide granules useful as a peroxide.
過酸化マグネシウム（ＭｇＯ２）は、マグネシウムの固形過酸化物であり、水には不溶だが、水分が存在すると徐々に分解して最終的に酸素を発生する。そうした特徴から、酸素供給剤として、土壌や地下水の改質、または汚染の浄化分野で活用されている。 Magnesium peroxide (MgO 2 ) is a solid peroxide of magnesium, which is insoluble in water, but gradually decomposes and finally generates oxygen when water is present. Because of such characteristics, it is used as an oxygen supply agent in the field of soil and groundwater reforming or pollution purification.
例として、主に油による汚染の浄化を目的とした酸素徐放剤として、現在最も広く用いられているのは過酸化マグネシウムを主成分とする製品ＯＲＣＴＭ（米国Ｒｅｇｅｎｅｓｉｓ社製）であり、白色の粉末状の薬剤であるＯＲＣＴＭは、地下水中や土壌中で酸素を長期間にわたって放出する（非特許文献１）。 As an example, the most widely used oxygen sustained-release agent mainly for the purification of oil contamination is the product ORC ™ (manufactured by Regenesis, USA), which is the most widely used at present. ORC TM , which is a powdered drug, releases oxygen over a long period of time in groundwater and soil (Non-patent Document 1).
また、農業分野での酸素供給剤として、過酸化マグネシウムの田水条件下での分解は、過酸化カルシウムより緩やかで、長期間にわたって徐々に、種子や農作物周辺に酸素を供給しつづけ得ることができる。過酸化カルシウムの分解過程で生成する水酸化カルシウムによる種子や農作物への薬害が発生することに比べ、過酸化マグネシウムの分解過程で生成する水酸化マグネシウムは、種子や農作物に対する薬害が発生する恐れは無い。さらに、マグネシウム元素が植物の葉緑素の中心金属であることから、農業分野ですでに使用されている過酸化カルシウムより、過酸化マグネシウムのほうがより有効な農業資材となると考えられ、農業場面での応用が望まれている。 In addition, as an oxygen supply agent in the agricultural field, decomposition of magnesium peroxide under paddy water conditions is slower than calcium peroxide and can continue to supply oxygen to seeds and crops gradually over a long period of time. it can. Compared to the chemical damage to seeds and crops caused by calcium hydroxide generated in the process of decomposition of calcium peroxide, magnesium hydroxide generated in the process of decomposition of magnesium peroxide is likely to cause chemical damage to seeds and crops. No. In addition, since magnesium element is the central metal of chlorophyll in plants, magnesium peroxide is considered to be a more effective agricultural material than calcium peroxide already used in the agricultural field. Is desired.
また、燃焼試験や落球試験による危険物判定では、過酸化カルシウムは有効酸素値５〜６％を超えると危険物に該当する傾向を示すのに対し、過酸化マグネシウムは有効酸素値１０％を超えて２０％近くのものでも危険物に該当しない。過酸化カルシウムより、過酸化マグネシウムは少量で多くの酸素を発生する高効率な酸素供給剤としても望ましい。 Moreover, in the dangerous substance judgment by the combustion test and the falling ball test, calcium peroxide tends to correspond to a dangerous substance when the effective oxygen value exceeds 5 to 6%, whereas magnesium peroxide exceeds the effective oxygen value of 10%. Nearly 20% of them are not classified as dangerous goods. Compared to calcium peroxide, magnesium peroxide is also desirable as a highly efficient oxygen supply that generates a large amount of oxygen in a small amount.
しかし、そうした分野においても、過酸化マグネシウムはほとんど使われていないのが現状である。不純物等に起因する純度や安定性の問題も考えられるが、大きな要因としては、連続的に大量生産ができる過酸化マグネシウム粒剤の製造方法が確立されていないためと推察される。有効酸素や含有金属元素の面で、むしろ劣ると思われる過酸化カルシウムが、すでに広く使われているのは、この過酸化物が容易に粒剤を製造でき、農業場面などでの取り扱いが容易なためである。 However, in such fields, magnesium peroxide is hardly used at present. Although the problem of the purity and stability resulting from an impurity etc. can also be considered, it is guessed that the manufacturing method of the magnesium peroxide granule which can mass-produce continuously is not established as a big factor. Calcium peroxide, which seems to be rather inferior in terms of effective oxygen and contained metal elements, is already widely used. This peroxide can easily produce granules and is easy to handle in agricultural situations. This is because of this.
また、生産工程上、過酸化マグネシウムを生成する反応は固体と液体の接触によって起こる反応であり、基本的にマグネシウムの水酸化物または酸化物の水媒体スラリーと過酸化水素の反応によって起こり、系内は反応の開始から終了までスラリー系である。したがって、反応後生成した過酸化マグネシウム製剤を乾燥させることも重要だが、造粒することによって、乾燥作業も容易になる。粒状であれば、より少ない時間やエネルギーコストで乾燥が可能な流動層乾燥機などが使用できるが、ケーキ状のまま乾燥させるとなると、金属バット等に広げて棚乾燥機などで乾燥させることになり、時間やエネルギーを多く使ってしまう。最終的に粉状で使いたい場合でも、いったん粒状で流動層乾燥機を用いて乾燥させた後、乾燥した粒状物を粉砕して粉状にするほうが、コスト的なメリットが大きい。 In addition, in the production process, the reaction for producing magnesium peroxide is a reaction that occurs due to contact between a solid and a liquid, and basically occurs due to the reaction between magnesium hydroxide or an oxide aqueous medium slurry and hydrogen peroxide. The inside is a slurry system from the start to the end of the reaction. Therefore, it is important to dry the magnesium peroxide formulation produced after the reaction, but the granulation facilitates the drying operation. If it is granular, a fluidized bed dryer that can be dried with less time and energy costs can be used, but when it is dried in a cake form, it is spread on a metal vat etc. and dried with a shelf dryer etc. It takes a lot of time and energy. Even when it is finally desired to use it in a powder form, it is more cost-effective if it is once granulated and dried using a fluidized bed dryer and then pulverized into a powder form.
上記の土壌改良分野や農業分野では、ハンドリングや飛散防止の面から、粉状ではなく、粒剤のほうが望ましい用途や用法も多い。そのため、過酸化マグネシウムの活用及び応用の展開に結びつく、効率的に大量生産ができる過酸化マグネシウム粒剤の製造方法が求められている。 In the above-mentioned soil improvement field and agricultural field, there are many applications and usages in which granules are desirable rather than powders in terms of handling and scattering prevention. Therefore, there is a demand for a method for producing magnesium peroxide granules that can be efficiently mass-produced, which leads to the utilization of magnesium peroxide and the development of applications.
過酸化マグネシウムの製造方法に関しては、すでにいくつかの報告が出ている（文献１〜７）。いずれの報告も、基本的には水溶媒中で水酸化マグネシウムと過酸化水素とを反応させるもので、水分を多量に含む形で生成する過酸化マグネシウムの乾燥に関しては、単に加熱してとしか記載が無く、それでは粉状の過酸化マグネシウムしか得られない。具体的に例を挙げると、特許文献６の実施例は、生成した過酸化マグネシウムの固形分を濾過して湿潤ケーキ（重量 約１９３ｇ）を得た。これを１０５℃の乾燥機で６ｈｒ乾燥し、約１０８ｇの乾燥品過酸化マグネシウムを得た。粒剤の過酸化マグネシウムを大量生産ができる製造方法に関しては、なんら言及がなされていない。 Several reports have already been issued regarding the production method of magnesium peroxide (References 1 to 7). Both reports basically involve reacting magnesium hydroxide and hydrogen peroxide in an aqueous solvent. Regarding the drying of magnesium peroxide produced in a form containing a large amount of water, it can only be heated. There is no description and only powdered magnesium peroxide is obtained. To give a specific example, in the example of Patent Document 6, the solid content of the produced magnesium peroxide was filtered to obtain a wet cake (weight: about 193 g). This was dried with a dryer at 105 ° C. for 6 hours to obtain about 108 g of a dried product magnesium peroxide. No mention is made of a manufacturing method capable of mass-producing granule magnesium peroxide.
実際に反応生成した過酸化マグネシウムからの水切れは悪く、遠心分離で含水率を３５重量％〜４５重量％まで低減することしかできないため、そのままの造粒が不可能であり、過酸化マグネシウム粒剤の製品化が実現できていない。一方、過酸化カルシウムでは、同じ操作で３５重量％未満にまで含水率を低減できるため、そのまま造粒が可能であり、過酸化カルシウム粒剤の製品化が実現できている。 The water breakage from the actually produced magnesium peroxide is poor, and the water content can only be reduced to 35 wt% to 45 wt% by centrifugation, so granulation as it is is impossible. Has not been commercialized. On the other hand, with calcium peroxide, the moisture content can be reduced to less than 35% by the same operation, so granulation is possible as it is, and commercialization of calcium peroxide granules has been realized.
過酸化マグネシウムの水切れの悪さを改善し、製造したままの状態で造粒ができるようになるため、炭酸マグネシウムなどの増量剤やカルボキシメチルセルロースなどの助剤添加により造粒する手段もあるが、非危険物、高有効酸素のメリットが活かせなくなる。一方、水分含量の多いケーキ状態のまま、乾燥処理を行なう手段もあるが、処理時間とコストが大きく掛かってしまう。水分含量が３５重量％未満となるようケーキ状で乾燥し、それを造粒、乾燥する手段は、やはり時間やコストの面では連続的な大量生産には不利であるため、実用的な過酸化マグネシウム粒剤の製品化に至らなかった。 Since it improves the poor drainage of magnesium peroxide and enables granulation in the as-manufactured state, there is a means to granulate by adding a bulking agent such as magnesium carbonate or an auxiliary agent such as carboxymethylcellulose. The merit of hazardous materials and high available oxygen can not be utilized. On the other hand, there is a means for performing a drying process in a cake state with a high water content, but the processing time and cost are greatly increased. The means for drying in the form of cake so that the water content is less than 35% by weight, and granulating and drying it is also disadvantageous for continuous mass production in terms of time and cost. The magnesium granule was not commercialized.
本発明は、高効率な酸素供給剤等とする過酸化マグネシウムに関し、その効率的に大量生産ができる過酸化マグネシウム粒剤の製造方法を提供する。 The present invention relates to magnesium peroxide used as a highly efficient oxygen supply agent and the like, and provides a method for producing magnesium peroxide granules capable of mass production efficiently.
本発明者らは、多量の水分を含んだ過酸化マグネシウムの反応生成物の含水率と、造粒性との関連を詳細に検討し、含水率によって造粒性に違いが出ることを発見した。そして、鋭意努力の結果、過酸化マグネシウムの造粒作業に好適な含水率の範囲、工業的に有利な含水率の調整方法、及び連続的に大量生産ができる過酸化マグネシウム粒剤の製造方法を見出し、本発明を完成させた。 The present inventors have studied in detail the relationship between the moisture content of the reaction product of magnesium peroxide containing a large amount of water and the granulation property, and found that the granulation property varies depending on the moisture content. . As a result of diligent efforts, a moisture content range suitable for magnesium peroxide granulation work, an industrially advantageous moisture content adjustment method, and a magnesium peroxide granule production method capable of continuous mass production. The headline and the present invention were completed.
すなわち、本発明は以下の構成を有する。 That is, the present invention has the following configuration.
[１] 含水率の調整工程、造粒工程及び乾燥工程を有する過酸化マグネシウム粒剤の製造方法であって、前記含水率の調整工程は、過酸化水素とマグネシウムの水酸化物または酸化物とを反応させて生成した過酸化マグネシウム（Ａ）の含水率を、１０重量％以上３５重量％未満となる範囲内に調整することを特徴とする含水率が１０重量％以下である過酸化マグネシウム粒剤の製造方法。
[２] 前記含水率の調整工程において、前記生成した過酸化マグネシウム（Ａ）の１００重量部に対し、含水率が１０重量％以下である過酸化マグネシウム（Ｂ）の３０〜７０重量部を混合することを特徴とする前記過酸化マグネシウム粒剤の製造方法。
[３] 前記含水率の調整工程において、前記生成した過酸化マグネシウム（Ａ）を脱水処理することにより、含水率を３５重量％から４５重量％までの範囲とした過酸化マグネシウム（Ｃ）の１００重量部に対し、前記過酸化マグネシウム（Ｂ）の３０〜７０重量部を混合することを特徴とする前記過酸化マグネシウム粒剤の製造方法。
[４] 前記過酸化マグネシウム（Ｂ）は[２]または[３]に記載の製造方法で得られた過酸化マグネシウム粒剤であることを特徴とする前記過酸化マグネシウム粒剤の製造方法。
[1] A method for producing a magnesium peroxide granule having a moisture content adjusting step, a granulating step, and a drying step, wherein the moisture content adjusting step includes hydrogen peroxide and magnesium hydroxide or oxide. Magnesium peroxide particles having a water content of 10% by weight or less, characterized in that the water content of the magnesium peroxide (A) produced by reacting is adjusted within a range of 10% by weight to less than 35% by weight Manufacturing method.
[2] In the water content adjusting step, 30 to 70 parts by weight of magnesium peroxide (B) having a water content of 10% by weight or less is mixed with 100 parts by weight of the produced magnesium peroxide (A). The manufacturing method of the said magnesium peroxide granule characterized by doing.
[3] Magnesium peroxide (C) 100 having a moisture content ranging from 35% to 45% by dehydrating the produced magnesium peroxide (A) in the moisture content adjusting step. The manufacturing method of the said magnesium peroxide granule characterized by mixing 30-70 weight part of the said magnesium peroxide (B) with respect to a weight part.
[4] The method for producing a magnesium peroxide granule, wherein the magnesium peroxide (B) is a magnesium peroxide granule obtained by the production method according to [2] or [3].
本発明の過酸化マグネシウム粒剤の製造方法は、工業的に実用な方法で過酸化マグネシウムの含水率を調整することによって、造粒工程は容易に実施できる。過酸化マグネシウムを造粒することで、乾燥工程の短時間化、省エネルギー化など、生産効率も図ることができる。こうしたことから、過酸化マグネシウム粒剤は連続的な大量生産が実現できる。したがって、過酸化カルシウムと比べ、有効酸素が高くかつ非危険物としやすい過酸化マグネシウムの特性を活かした粒剤として、様々な分野での実用化が期待できる。 As for the manufacturing method of the magnesium peroxide granule of this invention, a granulation process can be easily implemented by adjusting the moisture content of magnesium peroxide by an industrially practical method. By granulating magnesium peroxide, production efficiency such as shortening the drying process and saving energy can be achieved. For these reasons, the magnesium peroxide granule can be continuously mass-produced. Therefore, compared with calcium peroxide, it can be expected to be put to practical use in various fields as a granule utilizing the characteristics of magnesium peroxide, which has high effective oxygen and is easily non-hazardous.
以下、本発明を詳しく説明する。
過酸化マグネシウムは、前記の特許文献１〜７に基づき反応生成することができる。反応生成後の過酸化マグネシウム（Ａ）は多量の水分（５０重量％〜５５重量％の含水率）によってスラリー状なため、遠心分離機や吸引ろ過、あるいはニーダー等の脱水方法、あるいはそれらの組合せで脱水処理を行なう。一般的には、遠心分離による脱水で、反応生成後の過酸化マグネシウム（Ａ）の含水率をおおよそ３５重量％〜４５重量％の範囲に低減することができる。
The present invention will be described in detail below.
Magnesium peroxide can be produced by reaction based on the aforementioned Patent Documents 1-7. Magnesium peroxide (A) after the reaction is formed in a slurry state with a large amount of water (moisture content of 50% to 55% by weight), so a dehydration method such as a centrifuge, suction filtration, kneader, or a combination thereof Perform dehydration process. In general, the water content of the magnesium peroxide (A) after the reaction can be reduced to a range of approximately 35 wt% to 45 wt% by dehydration by centrifugation.
含水率を３５重量％〜４５重量％に低減した過酸化マグネシウム（Ｃ）でも、まだ造粒作業には含水率が過剰であり、造粒することは難しく、更に含水率を低減する必要がある。含水率が１０重量％を超え３５重量％未満、好ましくは２０重量％〜３０重量％の範囲内に調整すれば、造粒作業が可能になり、造粒物の乾燥作業も流動層乾燥機を用いることで容易に行われる。過酸化マグネシウムの含水率が３５重量％以上となると、造粒作業が困難となる。造粒処理前の含水率が１０重量％未満では、バインダの役割になる水の含有率が少なすぎるため、造粒作業は難しくなる傾向である。 Even with magnesium peroxide (C) whose moisture content has been reduced to 35% to 45% by weight, the moisture content is still excessive for granulation, it is difficult to granulate, and it is necessary to further reduce the moisture content. . If the water content exceeds 10% by weight and is less than 35% by weight, preferably adjusted within the range of 20% by weight to 30% by weight, granulation work becomes possible. Easy to use. If the moisture content of magnesium peroxide is 35% by weight or more, the granulation operation becomes difficult. If the water content before the granulation treatment is less than 10% by weight, the content of water serving as a binder is too small, and the granulation work tends to be difficult.
乾燥後粒剤の使用状況に応じて、さらに含水率の範囲を細かく調整することによって、乾燥後粒剤の安定性を制御することができる。例えば、乾燥後に粒剤のまま使用する場合、乾燥させた後の粒剤を崩れにくくするためには、造粒処理前の含水率が２４重量％〜３０重量％、好ましくは２６重量％〜３０重量％、特に好ましくは２７重量％〜２９重量％の範囲となるよう調整する必要がある。造粒処理前の含水率は２４重量％未満では、造粒工程は問題がないが、乾燥処理後の粒剤が崩れやすく、不安定である。３０重量％を超えると、ダマになり易い。なお、乾燥後に粉砕処理等で粉状化する場合には、特に支障ないため、造粒処理前の好適な含水率は１０重量％より多く２６重量％未満、好ましくは２０重量％〜２４重量％未満である。 The stability of the granules after drying can be controlled by finely adjusting the range of the moisture content according to the use conditions of the granules after drying. For example, when used as a granule after drying, the moisture content before granulation treatment is 24 wt% to 30 wt%, preferably 26 wt% to 30 wt%, in order to make the granule after drying difficult to collapse. It is necessary to adjust so that it may become the range of 27 weight%, especially preferably 27 weight%-29 weight%. If the moisture content before the granulation treatment is less than 24% by weight, there is no problem in the granulation step, but the granule after the drying treatment tends to collapse and is unstable. If it exceeds 30% by weight, it tends to become lumpy. In addition, in the case of pulverizing by drying or the like after drying, there is no particular problem, so a suitable water content before granulation is more than 10% by weight and less than 26% by weight, preferably 20% by weight to 24% by weight. Is less than.
しかし、過酸化マグネシウムの含水率が３５重量％未満となるよう調整することにおいて、遠心分離機や吸引ろ過、あるいはニーダー等の脱水方法を用いて、含水率を３５重量％未満まで効率的に低減することはなかなか困難である。反応生成した過酸化マグネシウムの固形分は微粉末であるので、フィルターは目詰まりし易く、濾過に時間がかかるので、濾過処理が困難である。この原因で、工業的に使われている遠心分離機や吸引ろ過等の脱水処理方法では生成した過酸化マグネシウムの含水率を効率よく３５重量％未満まで低減することが実現できない。 However, by adjusting the moisture content of magnesium peroxide to less than 35% by weight, the moisture content can be efficiently reduced to less than 35% by weight using a centrifugal separator, suction filtration, or a dehydration method such as a kneader. It is difficult to do. Since the solid content of the reaction-generated magnesium peroxide is a fine powder, the filter is likely to be clogged, and filtration takes time, so that filtration is difficult. For this reason, it is not possible to efficiently reduce the water content of the produced magnesium peroxide to less than 35% by weight by industrially used centrifugal separators and dehydration methods such as suction filtration.
遠心分離機や吸引ろ過等を用いて、反応生成した過酸化マグネシウム（Ａ）を脱水処理後、得た含水率が３５重量％〜４５重量％である過酸化マグネシウム（Ｃ）をケーキ状のままなどで直接加熱乾燥させ、含水率を１０重量％より多く３５重量％未満にまで水分を蒸発除去することもできる。しかし、その後の乾燥工程では、一般的には、金属バット等に該過酸化マグネシウムを適量取分け、棚乾燥機などで乾燥させることになる。この方法では、時間、手間のみならず、乾燥効率面からもかなりのエネルギーコストがかかり、効率のよい方法とは言えない。 After dehydrating the reaction-generated magnesium peroxide (A) using a centrifugal separator or suction filtration, the obtained magnesium peroxide (C) having a water content of 35% to 45% by weight remains in a cake form. It is possible to evaporate and remove the moisture by direct heating and drying to a moisture content of more than 10% by weight and less than 35% by weight. However, in the subsequent drying step, generally, an appropriate amount of the magnesium peroxide is separated into a metal bat or the like and dried with a shelf dryer or the like. This method requires considerable energy costs not only in terms of time and labor, but also in terms of drying efficiency, and is not an efficient method.
したがって、むしろ直接的に乾燥させて水分調整するよりは、別途用意しておいた乾燥度合いの高い過酸化マグネシウム（Ｂ）を脱水処理後の過酸化マグネシウム（Ｃ）に添加、混合させて、過酸化マグネシウム全体の含水率を１０重量％より多い３５重量％未満とすることが好ましい。この含水率の調整方法では、乾燥した過酸化マグネシウムであれば、粉状のものでも、粒状のものでも同様に用いることができる。 Therefore, rather than directly drying and adjusting the moisture, separately prepared magnesium peroxide (B) having a high degree of drying is added to and mixed with the magnesium peroxide (C) after the dehydration treatment. The moisture content of the entire magnesium oxide is preferably more than 10% by weight and less than 35% by weight. In this method for adjusting the water content, any powdered or granular material can be used as long as it is dry magnesium peroxide.
含水率調整用過酸化マグネシウム（Ｂ）は、理論上その含水率が３５重量％より低いものであれば用いることができるが、十分に含水率の低い過酸化マグネシウムでなければ、相対的にかなりの量の含水率調整用過酸化マグネシウム（Ｂ）が必要となり、含水率を調整する効率も良くなく、工業的に不向きである。したがって、予め乾燥された含水率調整用の過酸化マグネシウム（Ｂ）の含水率は、好ましくは１０重量％以下、より好ましくは５重量％以下である。 The water content adjusting magnesium peroxide (B) can theoretically be used as long as its water content is lower than 35% by weight. Thus, the amount of magnesium peroxide (B) for adjusting the water content is required, the efficiency of adjusting the water content is not good, and it is not industrially suitable. Therefore, the moisture content of the magnesium peroxide (B) for moisture content adjustment that has been dried in advance is preferably 10% by weight or less, more preferably 5% by weight or less.
反応生成した過酸化マグネシウム（Ａ）に直接含水率調整用過酸化マグネシウム（Ｂ）を添加し、含水率の調整もできるが、生成した過酸化マグネシウム（Ａ）の含水率はきわめて高い（５０重量％〜５５重量％）ので、一度脱水処理した後の過酸化マグネシウム（Ｃ）に含水率調整用過酸化マグネシウム（Ｂ）を添加するほうは生産効率が良い。脱水処理後の過酸化マグネシウム（Ｃ）の含水率はできるだけ低い方が好ましいが、大体３５重量％〜４５重量％の範囲になるので、水分調整用過酸化マグネシウム（Ｂ）の含水率および添加量によって、混合後の過酸化マグネシウムの含水率を意図的に調整することができる。 The water content can be adjusted by adding the water content adjusting magnesium peroxide (B) directly to the reaction-generated magnesium peroxide (A), but the water content of the generated magnesium peroxide (A) is very high (50 wt. % To 55% by weight), the production efficiency is better when the moisture content adjusting magnesium peroxide (B) is added to the magnesium peroxide (C) after dehydration once. The moisture content of magnesium peroxide (C) after dehydration is preferably as low as possible, but it is generally in the range of 35% to 45% by weight, so the moisture content and the amount of addition of magnesium peroxide (B) for moisture adjustment Thus, the moisture content of the magnesium peroxide after mixing can be intentionally adjusted.
過酸化マグネシウムの含水率の調整例として、反応生成した過酸化マグネシウム（Ａ）を脱水処理後、得た含水率４０重量％の過酸化マグネシウム（Ｃ）に、含水率５重量％の過酸化マグネシウム（Ｂ）を添加し、過酸化マグネシウム（Ｃ）と過酸化マグネシウム（Ｂ）の混合比率によって最終に得た過酸化マグネシウムの含水率が調整できる。例えば、（Ｃ）：（Ｂ）＝１００：４０の混合比率で得られる調整後の過酸化マグネシウムの含水率は３０重量％である。（Ｃ）：（Ｂ）＝１００：６７の混合比率で得られる調整後の過酸化マグネシウムの含水率は２６重量％である。 As an example of adjusting the moisture content of magnesium peroxide, magnesium peroxide (A) produced by the reaction was dehydrated, and the resulting magnesium peroxide (C) having a moisture content of 40% by weight was added to magnesium peroxide having a moisture content of 5% by weight. (B) can be added and the moisture content of the magnesium peroxide finally obtained can be adjusted with the mixing ratio of magnesium peroxide (C) and magnesium peroxide (B). For example, the moisture content of the adjusted magnesium peroxide obtained at a mixing ratio of (C) :( B) = 100: 40 is 30% by weight. The moisture content of the adjusted magnesium peroxide obtained at a mixing ratio of (C) :( B) = 100: 67 is 26% by weight.
過酸化マグネシウムを定常的に製造する場合は、前の生産ロットで出来た粉状もしくは粒状の乾燥な過酸化マグネシウムを適量取分けておき、含水率調整用過酸化マグネシウム（Ｂ）として、次の生産ロットで反応生成した過酸化マグネシウム（Ａ）を脱水処理した後の過酸化マグネシウム（Ｃ）に混合してやればよく、操作が簡単且つ連続的な作業ができ、工業的な生産においてたいへん有効な方法である。 When manufacturing magnesium peroxide on a regular basis, the appropriate amount of powdered or granular dry magnesium peroxide produced in the previous production lot is collected and used as magnesium peroxide (B) for moisture content adjustment. It is only necessary to mix magnesium peroxide (A) produced by reaction in the lot with magnesium peroxide (C) after dehydration, and it can be operated easily and continuously, and is a very effective method in industrial production. is there.
さらに具体に、本発明の製造方法において、前の生産ロットで得た乾燥された過酸化マグネシウム粒剤（製品）の一部を含水率調整用過酸化マグネシウム（Ｂ）として、次の生産ロットで反応生成した、脱水処理後の過酸化マグネシウム（Ｃ）に循環混合することで、該生産ロッドで生成した過酸化マグネシウムの造粒処理前の含水率を調整する。含水率調整用過酸化マグネシウム（Ｂ）として使用される過酸化マグネシウム粒剤製品は全部粒剤製品に対する割合（重量）は循環混合の割合と記載し、混合される過酸化マグネシウム（Ｂ）および（Ｃ）の含水率が低いほど、過酸化マグネシウム（Ｃ）に対する過酸化マグネシウム（Ｂ）の混合比率は低く、循環混合の割合も低いので、製品とする過酸化マグネシウム粒剤の割合は高くなり、製造効率は良くなる。 More specifically, in the production method of the present invention, a part of the dried magnesium peroxide granules (product) obtained in the previous production lot is used as the magnesium peroxide (B) for adjusting the water content in the next production lot. The water content before granulation of the magnesium peroxide produced by the production rod is adjusted by circulating and mixing with the magnesium peroxide (C) after the dehydration treatment produced by the reaction. Magnesium peroxide granule products used as the moisture content adjusting magnesium peroxide (B) are all described as the ratio of circulation mixing to the granule product (weight), and the mixed magnesium peroxide (B) and ( The lower the water content of C), the lower the mixing ratio of magnesium peroxide (B) to magnesium peroxide (C), and the lower the ratio of circulating mixing, the higher the ratio of magnesium peroxide granules used as products, Manufacturing efficiency is improved.
上記のことをもっと具体的に説明すると、例えば、脱水処理後の含水率が３５重量％である過酸化マグネシウム（Ｃ）に含水率調整用過酸化マグネシウム（Ｂ）として無水な過酸化マグネシウム粒剤を添加し、含水率を調整する場合、（１）（Ｃ）：（Ｂ）＝１００：５０の混合比率で連続生産すると、調整後含水率は２３％、循環混合の割合は４３％、製品とする粒剤の割合は５７％になる、（２）（Ｃ）：（Ｂ）＝１００：４０の混合比率で連続生産すると、調整後含水率は２５％、循環混合の割合は３８％、製品とする粒剤の割合は６２％になる、（３）（Ｃ）：（Ｂ）＝１００：３０の混合比率で連続生産すると、調整後含水率は２７％、循環混合の割合は３２％、製品とする粒剤の割合は６８％まで増加する。 The above will be described more specifically. For example, anhydrous magnesium peroxide granules as magnesium peroxide (B) for adjusting moisture content to magnesium peroxide (C) whose moisture content after dehydration is 35% by weight Is added to adjust the moisture content, (1) (C): (B) = 100: 50 continuous production, the adjusted moisture content is 23%, the circulation mixing ratio is 43%, the product The ratio of granules to be 57%, (2) (C): (B) = 100: 40, when continuously produced, the adjusted moisture content is 25%, the circulation mixing ratio is 38%, The ratio of the granule as a product is 62%. When continuously produced at a mixing ratio of (3) (C) :( B) = 100: 30, the adjusted moisture content is 27% and the ratio of circulating mixing is 32%. The proportion of granules as a product increases to 68%.
一方、脱水処理後含水率が４４重量％である過酸化マグネシウム（Ｃ）に含水率調整用過酸化マグネシウム（Ｂ）として無水な過酸化マグネシウム粒剤を添加し、含水率を調整する場合、（１）（Ｃ）：（Ｂ）＝１００：４０の混合比率で連続生産すると、調整後含水率は３１％、循環混合の割合は４２％、製品とする粒剤の割合は５８％である、（２）（Ｃ）：（Ｂ）＝１００：３０の混合比率で連続生産すると、調整後含水率は３４％、循環混合の割合は３５％、製品とする粒剤の割合は６５％まで増加する。 On the other hand, when anhydrous magnesium peroxide granules are added as magnesium peroxide (B) for moisture content adjustment to magnesium peroxide (C) whose moisture content after dehydration is 44% by weight, 1) When continuously produced at a mixing ratio of (C) :( B) = 100: 40, the adjusted moisture content is 31%, the ratio of circulating mixing is 42%, and the ratio of granules as products is 58%. (2) (C): (B) = Continuous production at a mixing ratio of 100: 30, the adjusted moisture content increases to 34%, the ratio of circulating mixing increases to 35%, and the ratio of granules to produce increases to 65% To do.
工業的な観点から見れば、循環混合の割合は少ないほど好ましいが、それは、過酸化マグネシウム（Ｃ）および過酸化マグネシウム（Ｂ）の含水率、また乾燥効率などから設定する調整後の目標含水率によって決まってくる。したがって、一概には言えないが、一般的には、本発明に於ける、含水率調整用過酸化マグネシウム（Ｂ）として使用する過酸化マグネシウム粒剤（製品）の循環混合の割合が５０％以下であることが好ましく、より好ましいのは４０％以下、特に好ましいのは３５％以下である。 From an industrial point of view, the smaller the ratio of circulating mixing, the better. However, it is the target water content after adjustment set from the water content of magnesium peroxide (C) and magnesium peroxide (B), and the drying efficiency. It depends on. Therefore, although it cannot be generally stated, generally, the ratio of the circulating mixture of magnesium peroxide granules (product) used as the moisture content adjusting magnesium peroxide (B) in the present invention is 50% or less. It is preferably 40% or less, more preferably 35% or less.
本発明にかかる過酸化マグネシウム粒剤の製造方法で連続生産の場合、過酸化マグネシウム粒剤（製品）の循環混合の割合が５０％より大きいのであれば、過酸化マグネシウム粒剤製品の割合は５０％以下になり、製造効率は低く、実用上は好ましくないと思われる。 In the case of continuous production by the method for producing a magnesium peroxide granule according to the present invention, if the ratio of the circulating mixture of magnesium peroxide granule (product) is greater than 50%, the proportion of the magnesium peroxide granule product is 50 % Or less, the production efficiency is low, and it is not preferable for practical use.
一方、過酸化マグネシウム粒剤（製品）の循環混合の割合が高くても、そうした混合を行なうことは、製造効率上、部分的な不利益をもたらすが、適量の循環混合の割合で粒剤製品を含水率調整用過酸化マグネシウム（Ｂ）として使用することにより、脱水処理または加熱処理のみで含水率を調整する作業に比べ、作業時間の短縮や消費エネルギーの低減が可能になり、かつ造粒ができるから、流動層乾燥機で造粒物を効率よく乾燥作業ができるので、作業時間および消費エネルギーを最適化することで、総合的にはコスト上有利なものとすることができる。 On the other hand, even if the ratio of circulating mixture of magnesium peroxide granules (product) is high, such mixing causes a partial disadvantage in terms of production efficiency. Can be used as magnesium peroxide (B) for adjusting the moisture content, so that the working time can be shortened and energy consumption can be reduced compared to the operation of adjusting the moisture content only by dehydration or heat treatment. Therefore, the granulated product can be efficiently dried with a fluidized bed dryer. Therefore, by optimizing the working time and energy consumption, the overall cost can be improved.
こうして含水率の調整を行なった過酸化マグネシウムは、容易に造粒作業を行なうことができる。造粒方法としては、ファインディスクペレッターや、少量であればツインドームグランを用いて行なう方法が確実であるが、特にこれらには限定されず、一般的な手法を用いて粒剤（ペレット）化できればいい。 Thus, the magnesium peroxide which adjusted the moisture content can be easily granulated. As a granulation method, a fine disc pelleter or a method using a twin dome granule if it is a small amount is reliable. However, the granulation method (pellet) is not limited to these, and a general method is used. It would be nice if it could be
造粒された過酸化マグネシウムは、乾燥工程において工業的に使われる乾燥機であれば良い。例えば、棚乾燥機でも流動層乾燥機でも使用できる、特に流動層乾燥機などで効率よく乾燥できるため、生産効率の向上や生産コストの低減が実現できる。 The granulated magnesium peroxide may be a drier used industrially in the drying process. For example, it can be used in either a shelf dryer or a fluidized bed dryer, and in particular, it can be efficiently dried with a fluidized bed dryer or the like, so that it is possible to improve production efficiency and reduce production costs.
乾燥条件に関して、特に限定することがなく、一般的に水分を効率良く蒸発できる条件であればよい。乾燥後の過酸化マグネシウム粒剤の含水率は、好ましく１０重量％以下、より好ましく５重量％以下である。 There is no particular limitation on the drying conditions, and any conditions that can evaporate water efficiently can be used. The moisture content of the magnesium peroxide granules after drying is preferably 10% by weight or less, more preferably 5% by weight or less.
乾燥後得た過酸化マグネシウム粒剤の粒径は、特に限定する必要がないが、応用分野の要求に応じて、製造工程により制御することができる。粒剤の粒径をコントロールする方法の一例として、原料である水酸化マグネシウムの粒径を変える方法がある。例えば、農業分野に好適な３μｍ〜７μｍの粒径範囲である過酸化マグネシウム粒剤を製造する場合には、３μｍ〜１０μｍサイズの水酸化マグネシウムを用いて製造すればよく、こうした粒径の水酸化マグネシウムは市販されている。 The particle size of the magnesium peroxide granules obtained after drying need not be particularly limited, but can be controlled by the production process according to the requirements of the application field. As an example of a method for controlling the particle size of the granule, there is a method of changing the particle size of magnesium hydroxide as a raw material. For example, when producing a magnesium peroxide granule having a particle size range of 3 μm to 7 μm suitable for the agricultural field, it may be produced using magnesium hydroxide having a size of 3 μm to 10 μm. Magnesium is commercially available.
水酸化マグネシウム（神島化学製）１７．６ｋｇ、６０％過酸化水素（保土谷化学製）２７．３４ｋｇを用い、文献６に記載された方法によって含水率４４重量％の過酸化マグネシウム（Ａ）３４ｋｇを得た。次いでＡＴ型遠心分離機（(株)田辺鉄工所）で１０分間脱水して含水率を４０重量％とした過酸化マグネシウム（Ｃ）を得た。これを金属バットに薄く均一に広げ、棚乾燥機を用いて９０℃で１時間乾燥した。含水率が３０重量％になった時点で、半量を取り分け、造粒機（ファインリューザーＥＸＲ−１００型、ダルトン製）で粒剤化し、半量の粉状物と半量の粒状物とも棚乾燥機で乾燥した。いずれも含水率が５重量％になるまで乾燥し、棚乾燥機で乾燥し続けた粉状物（６ｋｇ）と、途中粒剤化した粒状物（１２ｋｇ）を、含水率調整用の過酸化マグネシウム（Ｂ）とした。 Magnesium hydroxide (A) 34 kg having a moisture content of 44% by weight using the method described in Reference 6 using 17.6 kg of magnesium hydroxide (Kamishima Chemical), 27.34 kg of 60% hydrogen peroxide (Hodogaya Chemical) Got. Subsequently, it was dehydrated with an AT type centrifuge (Tanabe Iron Works Co., Ltd.) for 10 minutes to obtain magnesium peroxide (C) having a water content of 40% by weight. This was spread thinly and uniformly on a metal vat and dried at 90 ° C. for 1 hour using a shelf dryer. When the water content reaches 30% by weight, half the amount is separated and granulated with a granulator (FineLuser EXR-100 type, manufactured by Dalton), and both half amount of powder and half amount of granular material are shelf dryers. And dried. In both cases, the powdered product (6 kg) dried to a moisture content of 5% by weight and kept dry in a shelf dryer and the granulated product (12 kg) in the middle were used to adjust the moisture content. (B).
次いで、水酸化マグネシウム（神島化学製）２７．８ｋｇ、６０％過酸化水素（保土谷化学製）４３．２ｋｇを用い、同じ方法で含水率４０重量％の過酸化マグネシウム（Ｃ）５０ｋｇを得、これに上記の含水率調整用の過酸化マグネシウム（Ｂ）を次の表に示す条件で添加し、ニーダー（ＫＤＨＪ−２０型、富士パウダル製）で均一混合し、水分含量を調整した後、造粒機（ファインリューザーＥＸＲ−１００型、ダルトン製）を用いて造粒処理を行なった。得られた粒剤は連続乾燥の可否および乾燥後の粒剤の安定性について評価した。結果を、次の表１に示す。なお表１中に、過酸化マグネシウム（Ｂ）は（Ｂ）として記入し、過酸化マグネシウム（Ｃ）は（Ｃ）として記入する。 Then, 27.8 kg of magnesium hydroxide (manufactured by Kamishima Chemical) and 43.2 kg of 60% hydrogen peroxide (manufactured by Hodogaya Chemical) were used to obtain 50 kg of magnesium peroxide (C) having a water content of 40% by weight in the same manner. To this, magnesium peroxide (B) for adjusting the water content was added under the conditions shown in the following table, mixed uniformly with a kneader (KDHJ-20 type, manufactured by Fuji Powder), adjusted the water content, Granulation treatment was performed using a granulator (Finerewser EXR-100, manufactured by Dalton). The obtained granules were evaluated for the possibility of continuous drying and the stability of the granules after drying. The results are shown in Table 1 below. In Table 1, magnesium peroxide (B) is entered as (B), and magnesium peroxide (C) is entered as (C).
実施例４で得られた粒剤状の過酸化マグネシウム６．３ｋｇ（含水率５重量％）を初回生産によって得られた含水率調整用の過酸化マグネシウム（Ｂ）とし、次回生産分として、別途、水酸化マグネシウム（神島化学製）１７．６ｋｇ、６０％過酸化水素（保土谷化学製）２７．３４ｋｇを用い、上記と同じ方法で含水率４０重量％の過酸化マグネシウム（Ｃ）１９ｋｇを得た。過酸化マグネシウム（Ｃ）７ｋｇに対し、調整用の過酸化マグネシウム（Ｂ）３ｋｇを混合して含水率を３０％とし、造粒機（ファインリューザーＥＸＲ−１００型、ダルトン製）による造粒工程および流動層乾燥機による乾燥工程を実施し、含水率は５重量％である過酸化マグネシウムの粒剤６．５ｋｇを得た。ＳＥＭ観察の結果から、粒状形態は安定している（図１）。 The granule-shaped magnesium peroxide obtained in Example 4 (6.3 kg (water content 5% by weight)) was used as the magnesium peroxide (B) for adjusting the water content obtained by the first production, and separately for the next production. Using magnesium hydroxide (Kanshima Chemical Co., Ltd.) 17.6 kg, 60% hydrogen peroxide (Hodogaya Chemical Co., Ltd.) 27.34 kg, the same method as above was used to obtain 19 kg of magnesium peroxide (C) having a water content of 40% by weight. It was. Granulation process by granulating machine (Finerewser EXR-100 type, manufactured by Dalton) with mixing 3kg of magnesium peroxide (B) for adjustment to 7kg of magnesium peroxide (C) to make the water content 30%. And the drying process by a fluid bed dryer was implemented, and 6.5 kg of magnesium peroxide granules having a water content of 5% by weight were obtained. From the result of SEM observation, the granular form is stable (FIG. 1).
本発明によって、過酸化マグネシウムの粒剤は容易に連続生産を行なうことができ、粒剤の製品化が実現でき、農業分野や土壌改質分野における使用を促進することができる。また、造粒することで、乾燥工程の短時間化・省エネルギー化など、生産効率も図ることができる。こうしたことから、有効酸素が高い且つ非危険物としやすい過酸化マグネシウムの特性を活かした、扱いが容易な酸素供給剤等として有効な利用が可能となる。また、該粒剤は、過酸化マグネシウムの乾燥粉剤の原料としても実用性が高い。 According to the present invention, the magnesium peroxide granules can be easily continuously produced, the granules can be commercialized, and the use in the agricultural field and the soil reforming field can be promoted. Further, by granulating, it is possible to achieve production efficiency such as shortening the drying process and saving energy. For these reasons, effective use as an oxygen supply agent that is easy to handle and takes advantage of the characteristics of magnesium peroxide, which has high effective oxygen and is easily made non-hazardous, becomes possible. Moreover, the granule is highly practical as a raw material for dry powder of magnesium peroxide.
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