JP2763841B2 - Zeolite manufacturing method - Google Patents
Zeolite manufacturing methodInfo
- Publication number
- JP2763841B2 JP2763841B2 JP3349533A JP34953391A JP2763841B2 JP 2763841 B2 JP2763841 B2 JP 2763841B2 JP 3349533 A JP3349533 A JP 3349533A JP 34953391 A JP34953391 A JP 34953391A JP 2763841 B2 JP2763841 B2 JP 2763841B2
- Authority
- JP
- Japan
- Prior art keywords
- zeolite
- granulated slag
- sewage sludge
- ash
- cec
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Treatment Of Sludge (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、下水汚泥またはその焼
却灰を原料として付加価値の高い合成ゼオライトを製造
する方法に関するものである。The present invention relates to sewage sludge or its burning.
The present invention relates to a method for producing a high value-added synthetic zeolite using ashes as a raw material.
【０００２】[0002]
【従来の技術】ゼオライトは沸石と呼ばれる鉱物であ
り、 Me2/nO ・Al2O3 ・xSiO2 ・yH2O（Me：アルカリ又
はアルカリ土類、x,y ：係数）の一般式で表される三次
元結晶構造を有する含水アルミノケイ酸鉱物である。こ
のゼオライトは結晶内に多量の水分を含み、加熱したり
減圧するとこの水分を放出し、空になった結晶内に分子
を吸着する能力を持つことで知られている。BACKGROUND OF THE INVENTION Zeolites are minerals called zeolite, Me 2 / n O · Al 2 O 3 · xSiO 2 · yH 2 O (Me: alkaline or alkaline-earth, x, y: coefficient) by the general formula It is a hydrous aluminosilicate mineral having a three-dimensional crystal structure represented. This zeolite is known to contain a large amount of water in the crystal, release this water when heated or depressurized, and has the ability to adsorb molecules into the vacated crystal.
【０００３】一般にゼオライトの品質は塩基置換容量
（CEC)で評価され、比較的安価な天然ゼオライトはCEC
が150 meq/100g程度である。また、アルミン酸ナトリウ
ム、水酸化アルミニウム、シリカゲルを原料として工業
的に製造される合成ゼオライトはCEC が400 〜600 meq/
100gという優れた吸着性能を持つが、トン当りの価格が
数100 万円と極めて高価である欠点がある。[0003] Generally, the quality of zeolite is evaluated by base substitution capacity (CEC), and relatively inexpensive natural zeolite is CEC.
Is about 150 meq / 100g. The synthetic zeolite industrially produced from sodium aluminate, aluminum hydroxide and silica gel has a CEC of 400-600 meq /
It has an excellent adsorption performance of 100 g, but has the disadvantage that the price per ton is extremely high at several million yen.
【０００４】そこで最近では、特開平２−２２１１１４
号公報、特開平３−４０９１４号公報等に示されるよう
に、石炭灰から発生するフライアッシュをアルカリとと
もに煮沸してゼオライトを合成する方法が研究され、パ
イロットプラントが稼動している。しかしこの方法で合
成されたゼオライトのCEC はそのカタログ値によれば20
0 〜350 meq/100gであり、従来の合成ゼオライトよりも
安価である反面、CEC値が低いという問題がある。Therefore, recently, Japanese Patent Application Laid-Open No. Hei.
As disclosed in Japanese Patent Application Laid-Open No. HEI 3-40914, a method of synthesizing zeolite by boiling fly ash generated from coal ash together with alkali has been studied, and a pilot plant has been operated. However, the zeolite synthesized by this method has a CEC of 20
0 to 350 meq / 100 g, which is cheaper than the conventional synthetic zeolite, but has a problem that the CEC value is low.
【０００５】[0005]
【発明が解決しようとする課題】本発明は上記した従来
の問題点を解消し、CEC が合成ゼオライトと同程度であ
るゼオライトを極めて安価に製造することができるゼオ
ライトの製造法を提供するために完成されたものであ
る。SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned conventional problems and to provide a method for producing a zeolite capable of producing a zeolite having a CEC equivalent to that of a synthetic zeolite at extremely low cost. It is completed.
【０００６】[0006]
【課題を解決するための手段】上記の課題を解決するた
め、本発明者は無機分にSiO2、Al2O3 を主成分とする下
水汚泥に着目し、従来はその処分に困っていた下水汚泥
またはその焼却灰を原料としてゼオライトを合成できる
ことを見いだした。またフライアッシュを原料としたゼ
オライトのCEC が低いのは、フライアッシュ中にゼオラ
イトの生成に寄与するガラス状の成分が少ないことおよ
び生成物質と未生成物質との分離が困難であることが原
因であることを見いだした。本発明は上記した知見に基
づいて完成されたものであり、SiO2およびAl2O3 を含有
する下水汚泥またはその焼却灰を溶融して水砕スラグと
し、これに当量以上のアルカリを加えて煮沸してゼオラ
イトを生成し、得られたゼオライトを水砕スラグから分
離することを特徴とするものである。Means for Solving the Problems In order to solve the above problems, the present inventor has focused on sewage sludge containing SiO 2 and Al 2 O 3 as the main components of the inorganic component, and has conventionally been troubled with its disposal. Sewage sludge
Alternatively , they found that zeolite can be synthesized using the incinerated ash as a raw material. The low CEC of zeolite made from fly ash is also low due to the small amount of glassy components contributing to the formation of zeolite in fly ash and the difficulty in separating produced and unproduced substances. I found something. The present invention has been completed based on the above-described findings, and melts sewage sludge or incinerated ash containing SiO 2 and Al 2 O 3 into granulated slag, to which an equivalent or more of alkali is added. It is characterized by producing zeolite by boiling, and separating the obtained zeolite from granulated slag.
【０００７】上記したように、本発明においては原料と
してSiO2およびAl2O3 を含有する下水汚泥またはその焼
却灰を使用する。下水汚泥焼却灰は下水に添加される凝
集剤の種類によって高分子薬注汚泥焼却灰と塩鉄・石灰
薬注汚泥焼却灰とに大別されるが、前者はSiO2／Al2O3
の重量比が２〜４であり、かつ数％のCaO を含有するの
で、20〜30％ものCaO を含有する後者よりも原料として
適している。また高分子薬注汚泥焼却灰のうちでも、多
段炉焼却灰の方が流動炉焼却灰よりもガラス質が多く原
料として適している。As described above, in the present invention, sewage sludge containing SiO 2 and Al 2 O 3 as raw materials or its sewage sludge is used.
Use incinerated ash . Sewage sludge incineration ash is broadly classified into polymer-injected sludge incineration ash and salt iron / lime-injection sludge incineration ash, depending on the type of coagulant added to the sewage. The former is SiO 2 / Al 2 O 3
Is 2 to 4 and contains several% of CaO 2, so that it is more suitable as a raw material than the latter containing 20 to 30% of CaO 2. Also, among the sludge incineration ash of polymer chemicals, the multi-stage furnace incineration ash is more vitreous than the fluidized furnace incineration ash and is suitable as a raw material.
【０００８】本発明ではこのような下水汚泥焼却灰を、
例えば1200℃以上で溶融してガラス化したうえ、水中に
投入して急冷する。この結果、数mm〜数10mmの粒度分布
を持つ粒状の水砕スラグが得られるが、この水砕スラグ
はフライアッシュとは異なりムライト等の結晶部分がほ
とんどなく、100 ％に近い部分がゼオライト合成に適し
たガラス状物質である。また下水汚泥も1200℃以上で燃
焼溶融すると、上記と同様にガラス状物質となる。そこ
でこの水砕スラグにNaOHのようなアルカリを加え、例え
ば100 ℃で数時間煮沸するとゼオライトが水熱合成され
る。なおアルカリの量はSiO2とAl2O3 に対して当量以上
とすればよく、またその濃度も特に限定されないが、例
えば２Ｎのものを用いればよい。更に煮沸時間は長いほ
ど合成が進むが、工業的には３〜10時間が適当である。In the present invention, such sewage sludge incineration ash is
For example, it is melted and vitrified at 1200 ° C. or higher, and then put into water and quenched. As a result, granulated granulated slag having a particle size distribution of several mm to several tens of mm can be obtained. Unlike granulated slag, this granulated slag has almost no crystal part such as mullite, and the part close to 100% is composed of zeolite. It is a vitreous substance suitable for. Also, when sewage sludge is burned and melted at 1200 ° C. or higher, it becomes a glassy substance in the same manner as described above. Therefore, an alkali such as NaOH is added to the granulated slag, and the granulated slag is boiled at, for example, 100 ° C. for several hours, so that zeolite is hydrothermally synthesized. The amount of alkali may be at least equivalent to SiO 2 and Al 2 O 3 , and the concentration thereof is not particularly limited. For example, a 2N alkali may be used. Further, the longer the boiling time, the more the synthesis proceeds, but industrially, 3 to 10 hours is appropriate.
【０００９】合成されたゼオライトは粒径数μｍ以下の
微粉状であって、未反応の水砕スラグとは粒径が大きく
異なるので、例えば篩分けによって極めて容易に分離す
ることができる。また合成されたゼオライトの嵩比重は
0.3 前後と小さく、1.0 前後の嵩比重を持つ水砕スラグ
から比重差を利用した分離を行うことも容易である。従
って本発明によれば、純粋な合成ゼオライトのみを容易
に得ることができるのに対し、フライアッシュをNaOHと
ともに煮沸する方法で得られた従来の合成ゼオライトは
フライアッシュからの分離が困難であり、ゼオライト結
晶の含有比は50％程度にとどまっている。以下に本発明
を実施例によって更に詳細に説明する。The synthesized zeolite is in the form of a fine powder having a particle size of several μm or less, and has a particle size significantly different from that of unreacted granulated slag. Therefore, the zeolite can be separated very easily by, for example, sieving. The bulk specific gravity of the synthesized zeolite is
It is easy to separate from granulated slag with a specific gravity of around 1.0, which is as small as around 0.3 and has a bulk specific gravity of around 1.0. Therefore, according to the present invention, only pure synthetic zeolite can be easily obtained, whereas conventional synthetic zeolite obtained by boiling fly ash together with NaOH is difficult to separate from fly ash, The content ratio of zeolite crystals is only about 50%. Hereinafter, the present invention will be described in more detail with reference to Examples.
【００１０】[0010]
【実施例】高分子凝集剤を用いた下水汚泥を多段焼却炉
により焼却して下水汚泥焼却灰とした。その成分を分析
した結果は、SiO2 42.2 ％、Al2O3 15.2％、CaO 14.0
％、MgO 3.18 ％、Na2O 1.91 ％、K2O 1.60％、Fe 9.5
％であって、SiO2／Al2O3 ＝2.78であった。この下水汚
泥焼却灰を1200〜1300℃で溶融し、水中に投入して平均
粒径が５mm以下の水砕スラグとした。この水砕スラグに
２ＮのNaOHを十分量加え、大気圧中にて100 ℃で５時間
煮沸した。この結果、水砕スラグの表面のガラス状のSi
O2及びAl2O3 がNaOHと反応し、粒径数μｍの微粉状のゼ
オライトが水熱合成された。そこで合成されたゼオライ
トを篩によって水砕スラグから分離し、 NH3 + 吸着試験
によって吸着能を測定した。その結果を比較例とともに
表１に示す。EXAMPLE Sewage sludge using a polymer flocculant was incinerated by a multi-stage incinerator to produce sewage sludge incineration ash. The result of analyzing the components was SiO 2 42.2%, Al 2 O 3 15.2%, CaO 14.0%
%, MgO 3.18%, Na 2 O 1.91%, K 2 O 1.60%, Fe 9.5
%, And SiO 2 / Al 2 O 3 = 2.78. This sewage sludge incineration ash was melted at 1200 to 1300 ° C. and poured into water to obtain granulated slag having an average particle size of 5 mm or less. A sufficient amount of 2N NaOH was added to the granulated slag, and the slag was boiled at 100 ° C. for 5 hours under atmospheric pressure. As a result, the glassy Si on the surface of the granulated slag
O 2 and Al 2 O 3 reacted with NaOH, and zeolite in the form of fine powder having a particle size of several μm was hydrothermally synthesized. Then, the synthesized zeolite was separated from the granulated slag by a sieve, and the adsorption capacity was measured by an NH 3 + adsorption test. The results are shown in Table 1 together with Comparative Examples.
【００１１】[0011]
【表１】 ┌─────────────────┬──────────┐ │ 試 料 │ CEC （meq/100g）│ ├─────────────────┼──────────┤ │本発明品 │ 489 │ ├─────────────────┼──────────┤ │天然ゼオライト │ 150 │ │フライアッシュからの合成ゼオライト│ 146 │ │市販の合成ゼオライト │ 450 │ │Ａ │ 53 │ │Ｂ │ 18 │ │Ｃ │ 130 │ └─────────────────┴──────────┘[Table 1] ┌─────────────────┬──────────┐ │ Sample │ CEC (meq / 100g) │ ├──── │ │The present invention │ 489 │ ├───────────────── │ │ Natural zeolite │ 150 │ │ Synthetic zeolite from fly ash │ 146 │ │ Commercially available synthetic zeolite │ 450 │ │ A │ 53 │ │ B │ 18 │ │ C │ 130 │ └─────────────────┴──────────┘
【００１２】なお、表１においてＡ、Ｂ、Ｃはいずれも
下水汚泥焼却灰を水砕スラグ化することなく直接NaOH中
で煮沸して得られた合成ゼオライトを意味するもので、
Ａは高分子薬注汚泥を流動炉で焼却したもの、Ｂは塩鉄
・石灰汚泥を流動炉で焼却したもの、Ｃは高分子薬注汚
泥を多段炉で焼却したものを原料としたことを示してい
る。In Table 1, A, B, and C all mean synthetic zeolites obtained by boiling sewage sludge incineration ash directly in NaOH without forming granulated slag.
A is the incinerated polymer chemical sludge in a fluidized furnace, B is the incinerated salt iron / lime sludge in a fluidized furnace, and C is the incinerated polymeric chemical sludge in a multi-stage furnace. Is shown.
【００１３】本発明の方法により得られたゼオライト
は、上記した実施例のデータから明らかなように、フラ
イアッシュを原料として得られた合成ゼオライトよりも
はるかに高いCEC を示し、純物質を原料とする高価な合
成ゼオライトと同様以上のCECを示す。その理由は水砕
スラグ中でSiO2及びAl2O3 がほぼ完全にガラス化してい
るためアルカリに対する反応性に優れるためと、合成さ
れたゼオライトを未反応の水砕スラグから容易かつ完全
に分離することができ、純粋な合成ゼオライトを得られ
るためである。The zeolite obtained by the method of the present invention shows a much higher CEC than the synthetic zeolite obtained using fly ash as a raw material, as is apparent from the data of the above-mentioned examples, and a pure substance is used as a raw material. Exhibits a higher CEC than expensive synthetic zeolites. The reason is that SiO 2 and Al 2 O 3 are almost completely vitrified in the granulated slag, so that it has excellent reactivity with alkali.The synthesized zeolite is easily and completely separated from unreacted granulated slag. And a pure synthetic zeolite can be obtained.
【００１４】[0014]
【発明の効果】以上に説明したように、本発明は高価な
合成ゼオライトと同様以上のCEC を持つゼオライトを、
従来は処分に困っていた下水汚泥またはその焼却灰を原
料として極めて安価に製造することができるものである
から、従来の問題点を解消したゼオライトの製造法とし
て、産業の発展に寄与するところは極めて大である。As described above, the present invention provides a zeolite having a CEC equal to or higher than that of an expensive synthetic zeolite.
Since sewage sludge or its incinerated ash can be produced at very low cost as a raw material, which has been difficult to dispose of in the past, as a zeolite production method that solved the conventional problems, what contributes to industrial development is Very large.
Claims (2)
たはその焼却灰を溶融して水砕スラグとし、これに当量
以上のアルカリを加えて煮沸してゼオライトを生成し、
得られたゼオライトを水砕スラグから分離することを特
徴とするゼオライトの製造法。A sewage sludge containing SiO 2 and Al 2 O 3
Alternatively , the incinerated ash is melted into granulated slag, and an equivalent or more of alkali is added to the slag to boil to produce zeolite,
A method for producing zeolite, comprising separating the obtained zeolite from granulated slag.
その焼却灰を原料として用いる請求項１記載のゼオライ
トの製造法。 2. Sewage sludge or SiO 2 / Al 2 O 3 = 2-4.
The method for producing zeolite according to claim 1, wherein the incinerated ash is used as a raw material .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3349533A JP2763841B2 (en) | 1991-12-07 | 1991-12-07 | Zeolite manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3349533A JP2763841B2 (en) | 1991-12-07 | 1991-12-07 | Zeolite manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05155611A JPH05155611A (en) | 1993-06-22 |
| JP2763841B2 true JP2763841B2 (en) | 1998-06-11 |
Family
ID=18404370
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3349533A Expired - Fee Related JP2763841B2 (en) | 1991-12-07 | 1991-12-07 | Zeolite manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2763841B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6299854B1 (en) | 1998-06-12 | 2001-10-09 | Teruo Henmi | Method of producing artificial zeolite |
| JP2000335916A (en) * | 1999-05-31 | 2000-12-05 | Akio Henmi | Method and apparatus for producing artificial zeolite from slag |
| US6599494B2 (en) | 1999-08-19 | 2003-07-29 | K.E.M. Corporation | Process for preparing artificial zeolite by a slurry reaction method |
| JP2001089133A (en) * | 1999-09-28 | 2001-04-03 | Akio Henmi | Iron-containing artificial zeolite and method of producing the same |
| JP4246648B2 (en) * | 2004-02-16 | 2009-04-02 | 株式会社日立製作所 | Method for producing zeolitic modified soil |
| JP5399658B2 (en) * | 2007-08-03 | 2014-01-29 | プロメトロンテクニクス株式会社 | Method for producing artificial zeolite |
| JP5646807B2 (en) * | 2008-03-21 | 2014-12-24 | 株式会社ゼオライト・アーティフィシャル | Method for producing artificial zeolite |
| CN114377666A (en) * | 2022-01-28 | 2022-04-22 | 江西挺进环保科技股份有限公司 | Catalyst for inorganic ammonia nitrogen wastewater and wastewater treatment process |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6052087B2 (en) * | 1982-01-08 | 1985-11-18 | 幸雄 金治 | Manufacturing method of zeolitic composition |
-
1991
- 1991-12-07 JP JP3349533A patent/JP2763841B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05155611A (en) | 1993-06-22 |
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