JP2010111561A - Method for producing artificial zeolite using waste glass as raw material - Google Patents
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Abstract
Description
本発明はソーダ石灰ガラスから簡易に人工ゼオライトを製造する方法に関する。The present invention relates to a method for easily producing artificial zeolite from soda-lime glass.
廃棄物の有効利用として、近年、廃棄物を原料とする人工ゼオライト製造方法の開発が行われている。石炭灰から製造される人工ゼオライトにおいては実用化されており、溶融スラグからゼオライトを合成する方法も研究されている（逸見彰男著：無機系廃棄物の人工ゼオライト転換による有効利用）。In recent years, an artificial zeolite production method using waste as a raw material has been developed as an effective use of waste. Artificial zeolite produced from coal ash has been put into practical use, and a method for synthesizing zeolite from molten slag has been studied (Akio Iemi: Effective use of inorganic waste by converting artificial zeolite).
溶融スラグを原料とする場合、ゼオライト化を阻害するＣａ分を多量に含む場合が多く、Ｃａ分を除去した後にゼオライト化を行う製造方法が提案されている。When molten slag is used as a raw material, it often contains a large amount of Ca that inhibits zeolitization, and a production method has been proposed in which zeolitization is carried out after removing Ca.
特開０８−２５９２２１では高炉水砕スラグを原料とし、Ｃａ分を除去した後、ゼオライトを製造する方法が提案されている。それによれば、〈１〉スラグを１Ｎ以上の硫酸に溶解、〈２〉生成する石膏を分離、〈３〉ろ液をｐＨ３未満に調整、〈４〉生成するシリカゲルをろ過して分離、〈５〉そのろ液をｐＨ１３以上に調整、〈６〉重金属等の沈殿物を分離、〈７〉そのろ液をｐＨ４〜９に調整、〈８〉沈殿したアルミナを分離、〈９〉上記のシリカとアルミナにナトリウム分を調整し８５〜１５０℃、６〜１００時間の条件でゼオライトを水熱合成する。以上のような９工程を経てＡ型、またはＸ型のゼオライトを製造している。Japanese Patent Application Laid-Open No. 08-259221 proposes a method for producing zeolite after removing the Ca component from blast furnace granulated slag as a raw material. According to this, <1> slag is dissolved in 1N or more sulfuric acid, <2> the gypsum produced is separated, <3> the filtrate is adjusted to a pH of less than 3, <4> the produced silica gel is filtered and separated, <5 > Adjust the filtrate to pH 13 or higher, <6> Separate heavy metal precipitates, <7> Adjust the filtrate to pH 4-9, <8> Separate precipitated alumina, <9> The above silica and A zeolite is hydrothermally synthesized under conditions of 85 to 150 ° C. and 6 to 100 hours by adjusting sodium content in alumina. The A-type or X-type zeolite is manufactured through the above nine steps.
特開昭６０−１０８３５７では溶鉱炉スラグを原料として、〈１〉粉砕したスラグを廃硫酸（他用途で使用したもの）にｐＨ１．５前後で溶解、〈２〉生成した石膏をろ過、〈３〉ろ液に炭酸カルシウムを添加してｐＨ３．２前後に調整、〈４〉得られた石膏とシリカゲルの沈殿物のうち、浮遊法によってシリカゲル沈殿を分離、〈５〉シリカゲルろ過後のろ液にシリカ対アルミナの比が０．１になるように可溶性シリカを添加、〈６〉炭酸カルシウムを添加してｐＨ３．９に調整後、水酸化ナトリウムを添加してｐＨ４．６に調整、〈７〉アルミナゲルと石膏の沈殿物をろ過、〈８〉浮遊法によりアルミナゲルと石膏を分離、〈９〉上記のシリカゲル、アルミナゲルを水酸化ナトリウムでｐＨ１０まで中和、〈１０〉中和ゲル各々に一定量の水酸化ナトリウム溶液を添加し、アルミナゲルを溶解、〈１１〉アルミナゲルを溶解した溶液の重金属等の不溶解物をろ別、〈１２〉上記の二液を混合し、常温で一夜熟成、〈１３〉８５℃で２時間加熱して結晶化する。以上の１３工程を経て高炉スラグからＡ型ゼオライトを製造している。In JP-A-60-108357, using blast furnace slag as a raw material, <1> pulverized slag is dissolved in waste sulfuric acid (used in other applications) at a pH of about 1.5, <2> the produced gypsum is filtered, <3> Calcium carbonate is added to the filtrate to adjust the pH to around 3.2. <4> The silica gel precipitate is separated from the resulting gypsum and silica gel precipitate by the floating method. <5> Silica gel is added to the filtrate after silica gel filtration. Soluble silica was added so that the ratio of alumina to alumina was 0.1, <6> calcium carbonate was added to adjust to pH 3.9, sodium hydroxide was added to adjust to pH 4.6, <7> alumina Gel and gypsum precipitate are filtered, <8> Alumina gel and gypsum are separated by floating method, <9> Silica gel and alumina gel are neutralized to pH 10 with sodium hydroxide, <10> Constant for each neutralized gel amount Sodium hydroxide solution was added to dissolve the alumina gel, <11> the insoluble matter such as heavy metal in the solution in which the alumina gel was dissolved was filtered, <12> the above two solutions were mixed, and aged overnight at room temperature. 13> Crystallize by heating at 85 ° C. for 2 hours. A-type zeolite is manufactured from blast furnace slag through the above 13 steps.
特開昭５８−１２０５１２では水砕スラグ粉末を原料として、〈１〉水砕スラグ粉末を無機酸水溶液（硫酸を除く）に溶解、〈２〉アンモニアガスを吹き込んでｐＨを４〜９に調整、〈３〉沈殿物（シリカ、アルミナが主成分、カルシウム分は濾液側）をろ別、〈４〉沈殿物にアルカリを添加して１００〜１５０℃で５時間以上水熱合成する。以上の４工程を経てＡ型、またはＰ型のゼオライトを製造している。JP-A-58-120512 uses granulated slag powder as a raw material, <1> dissolved granulated slag powder in an inorganic acid aqueous solution (excluding sulfuric acid), <2> adjusted pH to 4-9 by blowing ammonia gas. <3> The precipitate (silica and alumina are the main components, calcium content is the filtrate side) is filtered off, <4> an alkali is added to the precipitate, and hydrothermal synthesis is performed at 100 to 150 ° C. for 5 hours or more. A-type or P-type zeolite is manufactured through the above four steps.
特開２００６−２３２５９７では、溶融還元スラグを原料とし、重金属の含有量がきわめて少ない安全な人工ゼオライトを製造することができ、さらに溶融還元スラグの原料として、生活ごみ、下水汚泥、産業廃棄物を焼却して生じた焼却灰および飛灰を用いることができ、廃棄物の有効利用を図ることができる。簡易な工程で、かつ短時間で製造することのできる、溶融還元スラグからの人工ゼオライトの製造方法を提供することである。
上記したようにＣａ分を含む溶融スラグを出発原料とする従来のゼオライト合成法は、ゼオライトの直接的な原料であるシリカ、アルミナをゼオライト化を阻害するＣａ分と分離するために多大な工程を必要としていた。また、溶融スラグを出発原料とする従来の水熱合成反応では、固体粉末と水酸化ナトリウム溶液との固液反応のため、ゼオライト化に５時間以上の長い時間を要していた。As described above, the conventional zeolite synthesis method using a molten slag containing Ca as a starting material requires a large number of steps to separate silica and alumina, which are direct raw materials of zeolite, from Ca that inhibits zeolitization. I needed it. Further, in the conventional hydrothermal synthesis reaction using molten slag as a starting material, a long time of 5 hours or more is required for the zeolitization because of the solid-liquid reaction between the solid powder and the sodium hydroxide solution.
溶融還元スラグを原料とすれば、重金属の含有量がきわめて少ない安全な人工ゼオライトを製造することができ、さらに溶融還元スラグの原料として、生活ごみ、下水汚泥、産業廃棄物を焼却して生じた焼却灰および飛灰を用いることができ、廃棄物の有効利用を図ることができるが、薬品を使用する多数の工程を要していた。Using smelted reduced slag as a raw material, it is possible to produce safe artificial zeolite with extremely low heavy metal content. In addition, as raw material for smelted reduced slag, it was generated by incineration of household waste, sewage sludge, and industrial waste. Incinerated ash and fly ash can be used, and waste can be effectively used, but many processes using chemicals are required.
本発明が解決しようとする課題は、上記従来技術の問題点を除き、原料として廃ガラスびんカレットと水だけを用い、簡易な工程で製造することのできる、ソーダ石灰ガラスからの人工ゼオライトの製造方法を提供することである。The problem to be solved by the present invention is the production of artificial zeolite from soda-lime glass that can be produced in a simple process using only waste glass bottle cullet and water as raw materials, except for the problems of the above-mentioned conventional techniques. Is to provide a method.
本願発明者は上記課題について検討した結果、粒径０．１５ｍｍの粉末ガラスと水道水のみを出発原料とした水熱合成反応を行うことによって上記課題の解決が可能であることを見出し、本発明に至った。すなわち、上記課題を解決するための手段として本願で特許請求される発明、もしくは少なくとも開示される発明は、以下のとおりである。
（１）ソーダ石灰ガラスと水だけを原料とし、水熱合成することを特徴とする人工ゼオライト製造方法。
（２）前記ソーダ石灰ガラスの粒径は０．１５ｍｍ以下であることを特徴とする、（１）に記載の人工ゼオライト製造方法。
（３）前記水熱合成の工程における加熱条件は、２００℃以上３００℃以下で加熱終了後は徐冷することを特徴とする、（１）に記載の人工ゼオライト製造方法。
（４）前記水熱合成の工程における加圧条件は、１ＭＰａ以上２０ＭＰａ以下であることを特徴とする、（１）に記載の人工ゼオライト製造方法。As a result of examining the above problems, the present inventor has found that the above problems can be solved by performing a hydrothermal synthesis reaction using only powder glass having a particle size of 0.15 mm and tap water as starting materials. It came to. That is, the invention claimed in the present application, or at least the disclosed invention, as means for solving the above-described problems is as follows.
(1) A method for producing artificial zeolite, characterized by hydrothermal synthesis using only soda-lime glass and water as raw materials.
(2) The artificial zeolite production method according to (1), wherein a particle size of the soda-lime glass is 0.15 mm or less.
(3) The method for producing an artificial zeolite according to (1), wherein the heating conditions in the hydrothermal synthesis step are 200 ° C. or more and 300 ° C. or less, and cooling is performed after the heating is completed.
(4) The artificial zeolite production method according to (1), wherein the pressurizing condition in the hydrothermal synthesis step is 1 MPa or more and 20 MPa or less.
本発明のソーダ石灰ガラスからの人工ゼオライトの製造方法は上述のように構成されるため、これによれば、廃ガラスびん微粉末と水だけを原料として、人工ゼオライトを簡易な工程で製造することができ、また、６〜１２時間の短い時間で水熱合成することができる。また、廃ガラスびんカレットをゼオライトの原料としているので、廃棄物の有効利用をはかれるという効果もある。Since the method for producing artificial zeolite from soda-lime glass of the present invention is configured as described above, according to this, artificial zeolite can be produced in a simple process using only waste glass bottle fine powder and water as raw materials. In addition, hydrothermal synthesis can be performed in a short time of 6 to 12 hours. In addition, since waste glass bottle cullet is used as a raw material for zeolite, there is an effect that waste can be effectively used.
以下、本発明をより詳細に説明する。
本発明では、一般家庭で排出される廃ガラスびんカレットを粒径０．１５ｍｍ以下に粉砕したものと水道水を水熱合成することを主たる構成とする。これにより薬品を使用した処理工程を含まないので、簡便で短時間でゼオライトを合成することができる。Hereinafter, the present invention will be described in more detail.
In the present invention, the main configuration is hydrothermal synthesis of a waste glass bottle cullet discharged from a general household and a tap water pulverized to a particle size of 0.15 mm or less. Since this does not include a treatment process using chemicals, it is possible to synthesize zeolite simply and in a short time.
より具体的には、〈１〉廃ガラスびんカレットを粒径０．１５ｍｍ以下になるように粉砕。〈２〉粉砕したソーダ石灰ガラスに水道水を加え２００℃以上に加熱し、５ＭＰａの圧力を加えて水熱合成を行う。以上の２工程により非常に簡便に人工ゼオライトを製造することができる。More specifically, <1> waste glass bottle cullet is pulverized to a particle size of 0.15 mm or less. <2> Tap water is added to the pulverized soda-lime glass, heated to 200 ° C. or higher, and hydrothermal synthesis is performed by applying a pressure of 5 MPa. An artificial zeolite can be produced very simply by the above two steps.
なお、ここでいう廃ガラスびんカレットとは、Ｓｉ分とＡｌ分とＮａ分Ｃａ分を含有した、ソーダ石灰ガラスのビンを粗粉砕したものを指し、重金属を多く含まないという特徴を有する。The waste glass bottle cullet here refers to a coarsely pulverized soda-lime glass bottle containing Si, Al and Na and Ca, and is characterized by not containing a lot of heavy metals.
廃ガラスびんカレットを粒径０．１５ｍｍ以下になるように粉砕したソーダ石灰ガラスの粉末はゼオライト化を進行させるため２００℃以上に加熱する。耐圧容器で密閉して５ＭＰａ以上に加圧できる装置で行うとよい。実際的には２００℃〜２５０℃で加熱処理することが望ましい。加熱時間は少なくとも６時間が必要である。本発明の方法であれば、少なくとも６時間加熱を行うことで人工ゼオライトを得ることができる。加熱時間は長時間であってもよいが、６〜１２時間程度の加熱で人工ゼオライトを充分に生成することができる。The soda-lime glass powder obtained by pulverizing the waste glass bottle cullet so as to have a particle size of 0.15 mm or less is heated to 200 ° C. or more in order to promote zeolitization. It is good to carry out by the apparatus which can be sealed with a pressure vessel and can be pressurized to 5 MPa or more. In practice, it is desirable to perform heat treatment at 200 ° C. to 250 ° C. The heating time needs at least 6 hours. With the method of the present invention, artificial zeolite can be obtained by heating for at least 6 hours. Although the heating time may be long, artificial zeolite can be sufficiently produced by heating for about 6 to 12 hours.
以下、本発明の実施例について説明する。
本発明の実施例に用いたガラスの主な組成はＳｉＯが６３％、Ｎａ２Ｏが１８％、ＣａＯが１３％、Ａｌ２Ｏ３が４％であった。Examples of the present invention will be described below.
The main composition of the glass used in the examples of the present invention was 63% SiO, 18% Na2O, 13% CaO, and 4% Al2O3.
＜実施例１＞
粉砕し粒径を０．７５ｍｍ以下としたソーダ石灰ガラス３５０ｇを肉厚０．１５ｍｍ、容量３５０ｍｌのアルミ製容器に入れた。これをステンレス製の加圧容器に入れ、水道水を９５０ｍｌ添加した。加圧容器を密閉した後、液温２００℃、圧力５ＭＰａで１２時間水熱反応した。その後、容器ごと徐冷した。容器内の水はＰＨ１１のアルカリ性を示す水ガラスが得られた。アルミ製容器から内部に生じた白色の固まりを取り出し、水洗、乾燥して白色の固形物を得た。
固形物を１０５℃で乾燥したもののかさ密度は１．３８ｇ／ｃｍ３であった。水蒸気を用いた等温吸着曲線からＢＥＴ法にて算定した比表面積は３５０ｍ２／ｇであった。
これを粉砕しＸ線回折したところ、モルデナイトを含むピークが見られた（図１）。なお、図２は得られた粉末の走査型電子顕微鏡写真である。
<Example 1>
350 g of soda lime glass having a particle diameter of 0.75 mm or less was pulverized and placed in an aluminum container having a wall thickness of 0.15 mm and a capacity of 350 ml. This was put into a stainless steel pressure vessel, and 950 ml of tap water was added. After the pressure vessel was sealed, hydrothermal reaction was performed at a liquid temperature of 200 ° C. and a pressure of 5 MPa for 12 hours. Thereafter, the entire container was gradually cooled. The water in the container was water glass showing PH11 alkalinity. A white lump produced inside was taken out from the aluminum container, washed with water and dried to obtain a white solid.
The bulk density of the solid dried at 105 ° C. was 1.38 g / cm 3 . The specific surface area calculated by the BET method from the isothermal adsorption curve using water vapor was 350 m 2 / g.
When this was pulverized and X-ray diffracted, a peak containing mordenite was observed ( FIG. 1 ). FIG. 2 is a scanning electron micrograph of the obtained powder.
本発明によれば廃ガラスびんカレットを原料として、ガラス粉末と水だけを原料として人工ゼオライトを簡易な工程で、かつ短い時間で製造することができる。また、重金属の含有量がきわめて少ない安全な人工ゼオライトが製造できる。したがって、産業上利用価値が高い発明である。According to the present invention, an artificial zeolite can be produced in a simple process and in a short time using waste glass bottle cullet as a raw material and only glass powder and water as raw materials. In addition, safe artificial zeolite with a very low content of heavy metals can be produced. Therefore, the invention has high industrial utility value.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5597298B1 (en) * | 2013-12-16 | 2014-10-01 | 長崎工業株式会社 | Zeolite structure |
| CN106865554A (en) * | 2015-12-12 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of glass refuse processing method |
| JP2019156785A (en) * | 2018-03-15 | 2019-09-19 | 学校法人 京都産業大学 | Antiseptic to influenza virus and its production method, and, deactivation method of influenza virus |
| CN111517292A (en) * | 2020-04-30 | 2020-08-11 | 西华大学 | Tin telluride-based thermoelectric material and preparation method thereof |
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2008
- 2008-11-07 JP JP2008310242A patent/JP2010111561A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5597298B1 (en) * | 2013-12-16 | 2014-10-01 | 長崎工業株式会社 | Zeolite structure |
| CN106865554A (en) * | 2015-12-12 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of glass refuse processing method |
| CN106865554B (en) * | 2015-12-12 | 2019-05-28 | 中国科学院大连化学物理研究所 | A kind of glass refuse processing method |
| JP2019156785A (en) * | 2018-03-15 | 2019-09-19 | 学校法人 京都産業大学 | Antiseptic to influenza virus and its production method, and, deactivation method of influenza virus |
| CN111517292A (en) * | 2020-04-30 | 2020-08-11 | 西华大学 | Tin telluride-based thermoelectric material and preparation method thereof |
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