JP2009227484A - Method for producing lithium-type zeolite - Google Patents
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- JP2009227484A JP2009227484A JP2008072014A JP2008072014A JP2009227484A JP 2009227484 A JP2009227484 A JP 2009227484A JP 2008072014 A JP2008072014 A JP 2008072014A JP 2008072014 A JP2008072014 A JP 2008072014A JP 2009227484 A JP2009227484 A JP 2009227484A
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Abstract
Description
本発明は、天然カオリナイトを焼成したメタカリオンを使用した、リチウム型ゼオライトの製造方法に係り、特に、アルカリ骨材反応を抑制するコンクリート材料に適するリチウム型ゼオライトの製造方法に関するものである。 The present invention relates to a method for producing a lithium type zeolite using metakalion obtained by calcining natural kaolinite, and more particularly to a method for producing a lithium type zeolite suitable for a concrete material that suppresses alkali aggregate reaction.
アルカリ骨材反応とは、コンクリート中の骨材の特定の鉱物とアルカリ性細孔溶液との間の化学反応によって、局部的な容積膨張が生じ、コンクリートにひび割れを生じさせるとともに、強度低下あるいは弾性の低下という物性の変化が生じる現象であり、道路・橋梁・トンネル・ビル等のコンクリート構造物の崩壊をもたらすことから社会的な問題となっている。この対策として、リチウム型ゼオライトがアルカリ骨材反応抑制に有効なことが報告されている。 Alkali-aggregate reaction refers to local volume expansion caused by a chemical reaction between a specific mineral of aggregate in the concrete and the alkaline pore solution, causing cracks in the concrete and reducing strength or elasticity. This is a phenomenon that causes a change in physical properties, such as a decline, and it is a social problem because it causes the collapse of concrete structures such as roads, bridges, tunnels, and buildings. As a countermeasure, it has been reported that lithium-type zeolite is effective in suppressing alkali-aggregate reaction.
かかるリチウム型ゼオライトはこれまでに、ABWゼオライトやEDIゼオライトなどの合成が報告されている(下記非特許文献1〜4参照)が、これらを製造するためには、アルミナゾル、シリカゾル、水酸化リチウムから調製したゲル、あるいは天然の粘土鉱物であるカオリナイトを焼成し活性化したメタカオリンあるいは天然粘土鉱物であるアロフェンに水酸化リチウム水溶液を加え、60℃〜200℃程度の高温条件下で合成された。あるいは、リチウム以外の金属を含むゼオライト(例えば、ナトリウム型ゼオライトA)を塩化リチウムなどのリチウム塩溶液中でイオン交換処理を数回繰り返した後、塩化物イオンを洗浄することにより製造されていた(下記特許文献1参照)。
しかしながら、従来のリチウム型ゼオライトの製造方法は、合成法においては高温条件下にすることが必要であり、イオン交換法においてはイオン交換操作の回数が多いため、コストが高いという問題があった。 However, the conventional method for producing lithium zeolite requires a high temperature condition in the synthesis method, and in the ion exchange method, the number of ion exchange operations is large.
また、リチウム型に限らず、ゼオライトの合成温度は80℃以上の報告が殆どであり、20℃〜50℃でのゼオライトの合成例は数少なく、それも極めて高いアルカリ濃度が必要か、あるいは合成時間が数カ月かち数年という極めて長くかかることから、工業的には現実的でないとされていた。 Moreover, not only the lithium type, the synthesis temperature of zeolite is mostly reported to be 80 ° C. or higher, and there are few examples of zeolite synthesis at 20 ° C. to 50 ° C., which also requires a very high alkali concentration, or the synthesis time. However, it took a very long time of several months to several years, so it was considered unrealistic industrially.
本発明は、上記状況に鑑みて、合成温度が20℃〜50℃の範囲で、しかも水酸化リチウムのアルカリ濃度が1M(1モル)と極めて希薄な濃度であり、短い合成時間で製造することができるリチウム型ゼオライトの製造方法を提供することを目的とする。 In view of the above situation, the present invention is manufactured in a short synthesis time with a synthesis temperature in the range of 20 ° C. to 50 ° C. and an alkali concentration of lithium hydroxide of 1M (1 mol). An object of the present invention is to provide a method for producing a lithium-type zeolite that can be used.
本発明は、上記目的を達成するために、
〔1〕リチウム型ゼオライトの製造方法において、天然の粘土鉱物であるカオリナイトを焼成し活性化したメタカオリンに水酸化リチウム水溶液を加え、20℃〜50℃の低温下の反応によって、アルカリ濃度が低く、しかも短い合成時間でリチウム型ゼオライトを製造することを特徴とする。
In order to achieve the above object, the present invention provides
[1] In a method for producing lithium zeolite, an aqueous lithium hydroxide solution is added to metakaolin obtained by calcining and activating kaolinite, a natural clay mineral, and the alkali concentration is lowered by a reaction at a low temperature of 20 ° C to 50 ° C. Moreover, it is characterized in that lithium zeolite is produced in a short synthesis time.
〔2〕上記〔1〕記載のリチウム型ゼオライトの製造方法において、前記メタカオリン1に対して、10倍量の1M(モル)水酸化リチウム水溶液を加えることを特徴とする。 [2] The method for producing a lithium zeolite according to [1] above, wherein 10 times the amount of 1M (mol) lithium hydroxide aqueous solution is added to the metakaolin 1.
〔3〕上記〔1〕又は〔2〕記載のリチウム型ゼオライトの製造方法において、前記水酸化リチウム水溶液を20℃〜50℃に調整した雰囲気中で24時間から120時間保持することを特徴とする。 [3] The method for producing a lithium zeolite according to [1] or [2], wherein the lithium hydroxide aqueous solution is maintained in an atmosphere adjusted to 20 ° C. to 50 ° C. for 24 hours to 120 hours. .
〔4〕上記〔1〕、〔2〕又は〔3〕記載のリチウム型ゼオライトの製造方法において、前記メタカオリン1に対して10倍量の1M(モル)水酸化リチウム水溶液を加え、密閉容器に入れ、この密閉容器を20℃〜50℃に調整した雰囲気中で24時間から120時間保持し、該保持時間が経過した後、得られた沈殿物を常温でろ過・洗浄・乾燥し、白色粉末からなるリチウム型ゼオライトを得ることを特徴とする。 [4] In the method for producing a lithium-type zeolite described in [1], [2] or [3] above, 10 times the amount of 1M (mol) lithium hydroxide aqueous solution is added to the metakaolin 1, and the mixture is placed in a sealed container. The sealed container is held in an atmosphere adjusted to 20 ° C. to 50 ° C. for 24 to 120 hours, and after the holding time has elapsed, the resulting precipitate is filtered, washed and dried at room temperature to obtain a white powder. A lithium type zeolite is obtained.
本発明によれば、次のような効果を奏することができる。 According to the present invention, the following effects can be achieved.
(1)20℃〜50℃という極めて低温でリチウム型ゼオライトが合成できる。 (1) Lithium-type zeolite can be synthesized at an extremely low temperature of 20 ° C to 50 ° C.
(2)メタカオリンは安価(100〜150円/kg)であり、合成コストが低い。 (2) Metakaolin is inexpensive (100 to 150 yen / kg) and the synthesis cost is low.
(3)メタカオリンは鉄等の着色不純物が極めて少ないため、白色度の高い、リチウム型ゼオライトが得られる。 (3) Since metakaolin has very little colored impurities such as iron, a lithium zeolite with high whiteness can be obtained.
本発明のリチウム型ゼオライトの製造方法は、天然の粘土鉱物であるカオリナイトを焼成し活性化したメタカオリンに水酸化リチウム水溶液を加え、20℃〜50℃の低温下の反応によって、リチウム型ゼオライトを製造する。 According to the method for producing a lithium zeolite of the present invention, a lithium hydroxide aqueous solution is added to metakaolin obtained by calcining and activating kaolinite, which is a natural clay mineral, and a reaction at a low temperature of 20 ° C. to 50 ° C. To manufacture.
以下、本発明の実施の形態について詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
本発明のリチウム型ゼオライトの製造方法は、天然の粘土鉱物であるカオリナイトを焼成し活性化したメタカオリンに水酸化リチウム水溶液を加え、20℃〜50℃の低温下の反応によって、リチウム型ゼオライトを製造する。 According to the method for producing a lithium zeolite of the present invention, a lithium hydroxide aqueous solution is added to metakaolin obtained by calcining and activating kaolinite, which is a natural clay mineral, and a reaction at a low temperature of 20 ° C. to 50 ° C. To manufacture.
図1は本発明の実施例に係るリチウム型ゼオライトの製造装置を示す図、図2は本発明の実施例のリチウム型ゼオライトの製造方法を示すフローチャートである。 FIG. 1 is a diagram showing an apparatus for producing a lithium zeolite according to an embodiment of the present invention, and FIG. 2 is a flowchart showing a method for producing a lithium zeolite according to an embodiment of the present invention.
図1において、1は密閉容器、2は密閉容器1内の沈殿物、3は電子制御装置、4は制御部、5は温度調整装置、6は計時装置、7は沈殿物2の排出口、7Aは電磁開閉弁、8はろ過・洗浄・乾燥処理装置、8Aは送出装置、9はろ過・洗浄・乾燥処理装置8の排出口、9はそのろ過・洗浄・乾燥処理装置8の排出口、10は排出口9から得られた白色粉末である。
In FIG. 1, 1 is an airtight container, 2 is a deposit in the airtight container 1, 3 is an electronic control device, 4 is a control unit, 5 is a temperature adjusting device, 6 is a timing device, 7 is an outlet for the
以下、リチウム型ゼオライトの製造方法について図2に示すフローチャートを参照しながら説明する。 Hereinafter, a method for producing lithium zeolite will be described with reference to the flowchart shown in FIG.
(1)まず、天然カオリナイトを焼成したメタカオリン(モル)1に対し、10倍量の水酸化リチウム(モル)の水溶液を、密閉容器1中で混合する(ステップS1)。 (1) First, 10 times the amount of lithium hydroxide (mol) aqueous solution is mixed in the closed container 1 with respect to metakaolin (mol) 1 obtained by firing natural kaolinite (step S1).
(2)この密閉容器1を温度調整装置5により20℃〜50℃に調整した雰囲気中で計時装置6で監視して24時間から120時間保持する(ステップS2)。
(2) The airtight container 1 is monitored by the time measuring device 6 in an atmosphere adjusted to 20 ° C. to 50 ° C. by the temperature adjusting
(3)再び、天然カオリナイトを焼成したメタカオリン(モル)1に対し、10倍量の水酸化リチウム(モル)の水溶液を、密閉容器1中で混合する(ステップS3)。 (3) Again, an aqueous solution of 10 times the amount of lithium hydroxide (mol) is mixed in the closed container 1 with respect to metakaolin (mol) 1 obtained by firing natural kaolinite (step S3).
(4)所定の時間が経過した後、得られた沈殿物2をろ過・洗浄・乾燥処理装置8において常温でろ過・洗浄・乾燥する(ステップS4)。
(4) After a predetermined time has elapsed, the obtained
(5)回収水酸化リチウム水溶液+未使用水酸化リチウム水溶液を再利用する(ステップS5)。 (5) The recovered lithium hydroxide aqueous solution + unused lithium hydroxide aqueous solution is reused (step S5).
(6)ステップS4により、白色粉末10が得られる(ステップS6)。
(6) The
このようにした製造された白色粉末10を、X線回折法により回折した結果、リチウム型ゼオライト(Li−EDI、Li−EDI+Li−ABW)であることを確認できた。
As a result of diffracting the produced
かかるリチウム型ゼオライトは、アルカリイオン捕集機能を有し、リチウムイオンの効果と相まってアルカリ骨材反応を抑制する材料(例えば、コンクリート材料)として好適である。
〔実施例1〕
メタカオリン1gに対し、1M(モル)の水酸化リチウム水溶液10mlを加え、テフロン(登録商標)性の密閉容器内で、30℃、24時間反応を行った。反応後、生成物を蒸留水で洗浄し、乾燥した。得られた生成物をX線回折により調べた結果、リチウム型EDIゼオライトの生成を確認した。
〔実施例2〕
メタカオリン1gに対し、1M(モル)の水酸化リチウム水溶液10mlを加え、テフロン(登録商標)性の密閉容器内で、50℃、120時間反応を行った。反応後、生成物を蒸留水で洗浄し、乾燥した。得られた生成物をX線回折により調べた結果、リチウム型ABWゼオライトとリチウム型EDIゼオライトの混合物であることを確認した。
Such lithium-type zeolite has an alkali ion collecting function and is suitable as a material (for example, a concrete material) that suppresses the alkali aggregate reaction in combination with the effect of lithium ions.
[Example 1]
To 1 g of metakaolin, 10 ml of a 1M (mol) lithium hydroxide aqueous solution was added, and the reaction was performed at 30 ° C. for 24 hours in a Teflon (registered trademark) sealed container. After the reaction, the product was washed with distilled water and dried. As a result of examining the obtained product by X-ray diffraction, it was confirmed that lithium type EDI zeolite was produced.
[Example 2]
To 1 g of metakaolin, 10 ml of a 1M (mol) lithium hydroxide aqueous solution was added, and the reaction was carried out at 50 ° C. for 120 hours in a Teflon (registered trademark) sealed container. After the reaction, the product was washed with distilled water and dried. As a result of examining the obtained product by X-ray diffraction, it was confirmed that it was a mixture of lithium ABW zeolite and lithium EDI zeolite.
これまでカオリナイトもしくはメタカオリンを原料とした、リチウム型ゼオライトの合成例において、EDIゼオライトは報告されておらず、本発明において初めてリチウム型EDIゼオライトの合成に成功した。また、その合成温度は、これまで化成原料(アルミナゾル、シリカゾル)やアロフェンからのEDIゼオライトの合成温度である60〜100℃よりも極めて低い、20℃〜50℃である。 So far, no EDI zeolite has been reported in the synthesis examples of lithium zeolite using kaolinite or metakaolin as a raw material, and for the first time in the present invention, lithium type EDI zeolite was successfully synthesized. The synthesis temperature is 20 ° C. to 50 ° C., which is much lower than 60 to 100 ° C., which is the synthesis temperature of EDI zeolite from chemical raw materials (alumina sol, silica sol) and allophane.
また、本発明ではリチウム型ABWゼオライトとリチウム型EDIゼオライトの混合物も得られているが、ABWゼオライトの合成温度に関しても、従来報告されている80℃〜200℃と比較して低い合成温度に成功している。 In the present invention, a mixture of lithium-type ABW zeolite and lithium-type EDI zeolite was also obtained, but the synthesis temperature of ABW zeolite was also successful at a low synthesis temperature compared to 80 ° C. to 200 ° C. reported conventionally. is doing.
このように、本発明によれば、天然カオリナイトを焼成したメタカオリンを使用して、これまでより安価にリチウム型ゼオライトを製造する条件を見出した。また、イオン種の異なるゼオライトを使用して煩雑なイオン交換、洗浄を繰り返す必要もない。 Thus, according to the present invention, the present inventors have found conditions for producing lithium-type zeolite at a lower cost than before by using metakaolin obtained by calcining natural kaolinite. Further, it is not necessary to repeat complicated ion exchange and washing using zeolites having different ionic species.
なお、本発明は上記実施例に限定されるものではなく、本発明の趣旨に基づいて種々の変形が可能であり、これらを本発明の範囲から排除するものではない。 In addition, this invention is not limited to the said Example, A various deformation | transformation is possible based on the meaning of this invention, and these are not excluded from the scope of the present invention.
本発明のリチウム型ゼオライトの製造方法は、安価にしかも容易にアルカリ骨材反応を抑制するコンクリート材料に適するリチウム型ゼオライトの製造を行うために利用することができる。 The method for producing a lithium-type zeolite of the present invention can be used for producing a lithium-type zeolite suitable for a concrete material that can easily inhibit the alkali-aggregate reaction at low cost.
1 密閉容器
2 密閉容器内の沈殿物
3 電子制御装置
4 制御部
5 温度調整装置
6 計時装置
7 沈殿物の排出口
7A 電磁開閉弁
8 ろ過・洗浄・乾燥処理装置
8A 送出装置
9 ろ過・洗浄・乾燥処理装置の排出口
10 白色粉末
DESCRIPTION OF SYMBOLS 1
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JP2013237585A (en) * | 2012-05-15 | 2013-11-28 | Tochigi Prefecture | Abw type zeolite, alkali-silica reaction inhibiting material using the same, and production methods thereof |
CN113264538A (en) * | 2021-05-29 | 2021-08-17 | 山西腾茂科技股份有限公司 | Preparation method and application of molecular sieve adsorbent based on LiNaKLSX |
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JP2013237585A (en) * | 2012-05-15 | 2013-11-28 | Tochigi Prefecture | Abw type zeolite, alkali-silica reaction inhibiting material using the same, and production methods thereof |
CN113264538A (en) * | 2021-05-29 | 2021-08-17 | 山西腾茂科技股份有限公司 | Preparation method and application of molecular sieve adsorbent based on LiNaKLSX |
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