JP4819376B2 - Treatment method for fluororesin-containing materials - Google Patents
Treatment method for fluororesin-containing materials Download PDFInfo
- Publication number
- JP4819376B2 JP4819376B2 JP2005065400A JP2005065400A JP4819376B2 JP 4819376 B2 JP4819376 B2 JP 4819376B2 JP 2005065400 A JP2005065400 A JP 2005065400A JP 2005065400 A JP2005065400 A JP 2005065400A JP 4819376 B2 JP4819376 B2 JP 4819376B2
- Authority
- JP
- Japan
- Prior art keywords
- fluororesin
- fluorine
- containing material
- raw material
- cement raw
- 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.)
- Active
Links
Description
本発明は、フッ素系樹脂含有物の処理方法に関する。詳しくは、本発明はフッ素系樹脂含有物をセメント原料化することで安全に処理して、処理時に有害なフッ酸が発生しないような処理方法に関する。 The present invention relates to a method for treating a fluororesin-containing material. Specifically, the present invention relates to a treatment method in which a fluorine-containing resin-containing material is safely treated by making it into a cement raw material so that no harmful hydrofluoric acid is generated during the treatment.
フッ素系樹脂は焼却処分すると、有害なフッ酸が発生するために、通常の焼却処理ができず、埋立処理または、焼却時に発生するフッ酸を分離・吸収するような特殊な機能を持った焼却炉で処分されていた。また、特開平６−２４１４３３号公報（特許文献1）では特殊な燃焼条件によりフッ素系樹脂を無公害的にガス化減容する方法を提供しているが、処理条件が複雑であり、平易にはフッ素系樹脂を焼却処分することが難しい。
本発明は、フッ素系樹脂含有物をセメント原料化することで安全に処理して、処理時に有害なフッ酸が発生しないような処理方法を提供することを目的とする。 An object of the present invention is to provide a treatment method in which a fluorine-containing resin-containing material is safely treated by making it into a cement raw material so that no harmful hydrofluoric acid is generated during the treatment.
本発明者は、フッ素系樹脂含有物を安全に処理する方法について、鋭意研究を重ねた結果、フッ素系樹脂含有物を、セメント原料と共にキルン中に投入処理し、最終的にセメント原料化することでフッ素系樹脂を無害に処理する方法を見出した。セメントの原料工程でフッ素系樹脂含有物を、セメント原料と共にキルン中に投入し焼成すると、セメント原料中のカルシウム化合物とフッ素系樹脂の燃焼で発生したフッ酸が直ちに反応して無害なフッ化カルシウム（ＣａＦ２）となることより、フッ素系樹脂含有物を簡単かつ安全に処理することを可能とした。また、反応で生成したフッ化カルシウムはそのままセメント原料となるので廃棄物を有効利用することができる。 As a result of intensive research on the method of safely treating fluorine-containing resin-containing materials, the present inventor puts the fluorine-containing resin-containing materials into a kiln together with cement raw materials, and finally converts them into cement raw materials. And found a method for harmless treatment of fluororesin. When the fluororesin-containing material is put into the kiln together with the cement raw material in the cement raw material process and calcined, the calcium compound in the cement raw material and the hydrofluoric acid generated by the combustion of the fluororesin react immediately and harmless calcium fluoride. By being (CaF 2 ), the fluorine-containing resin-containing material can be easily and safely treated. Moreover, since the calcium fluoride produced | generated by reaction becomes a cement raw material as it is, waste can be used effectively.
すなわち、本発明は下記の通りである。
フッ素系樹脂含有物を粉砕してプレヒーターで予熱し、
予熱した前記フッ素系樹脂含有物を、プレヒーターで予熱したセメント原料と共にキルン中に投入し燃焼処理することで、前記フッ素系樹脂含有物をセメント原料化することを特徴とするフッ素系樹脂含有物の処理方法。
また、前記フッ素系樹脂含有物は、フッ素系樹脂として、ポリフッ化ビニリデン、ポリテトラフルオロエチレン、ポリクロロトリフルオロエチレン、又はエチレンテトラフルオロエチレンのうち少なくとも１種を含有することとしてもよい。
また、前記フッ素系樹脂含有物は、中空糸状の多孔質膜の形態を有することが好ましい。
また、前記セメント原料と共に前記キルン中に投入される前記フッ素系樹脂含有物の量が、前記セメント原料の重量に対して５重量％以下であることが好ましい。
That is, the present invention is as follows.
Crush the fluororesin-containing material and preheat it with a preheater.
The fluorine-based resin-containing material preheated, by charged and be combusted in the kiln together with the preheated cement material in a preheater, a fluorine-based resin-containing product of the fluorine-based resin-containing material, characterized in that raw material for cement Processing method .
The fluororesin-containing material may contain at least one of polyvinylidene fluoride, polytetrafluoroethylene, polychlorotrifluoroethylene, or ethylenetetrafluoroethylene as the fluororesin.
Moreover, it is preferable that the said fluororesin containing material has a form of a hollow fiber-like porous membrane.
Moreover, it is preferable that the quantity of the said fluororesin containing material thrown into the said kiln with the said cement raw material is 5 weight% or less with respect to the weight of the said cement raw material.
本発明によれば、フッ素系樹脂含有物を、セメント原料と共にキルン中に投入処理し、最終的にセメント原料化することでフッ素系樹脂を簡単かつ安全に処理することができる。 According to the present invention, the fluororesin can be easily and safely treated by introducing the fluororesin-containing material into the kiln together with the cement raw material and finally converting it into a cement raw material.
本発明について、以下具体的に説明する。本発明方法を適用することができるフッ素系樹脂はＰＶＤＦ（ポリフッ化ビニリデン）、ＰＴＦＥ（ポリテトラフルオロエチレン）、ＰＣＴＦＥ（ポリクロロトリフルオロエチレン）、ＥＴＦＥ（エチレンテトラフルオロエチレン）など分子中にフッ素原子を含有するポリマーが該当する。フッ素系樹脂含有物は特に制限がなく、例えば、フッ素系樹脂を主原料とした成形品などで、形態としてはプラスチック製品のような任意の形状の成形物、繊維状、中空糸状に加工されたものであっても、成形前のペレット状、パウダー状のものであってもよい。 The present invention will be specifically described below. The fluorine resin to which the method of the present invention can be applied is a fluorine atom in the molecule such as PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), PCTFE (polychlorotrifluoroethylene), ETFE (ethylenetetrafluoroethylene), etc. Applicable to polymers containing The fluororesin-containing material is not particularly limited, and is, for example, a molded product made of a fluororesin as a main raw material, and is processed into a molded product having an arbitrary shape such as a plastic product, a fibrous shape, or a hollow fiber shape. Even if it is a thing, the thing of the pellet form before shaping | molding and a powder form may be sufficient.
特に、フッ素系樹脂が中空糸状の多孔質膜の形態を有しておれば、表面積が多くなっているために、フッ素系樹脂の燃焼時に発生するフッ酸とセメント原料中のカルシウム化合物との反応が容易に進むために好ましい。更に、より安全に処理を行うためには、フッ素系樹脂含有物にカルシウム化合物を含んだ溶液を事前に含浸させても良い。また、フッ素系樹脂以外の成分としては、フッ素系樹脂の成形時に一般的に使用される可塑剤や無機フィラーなどを含んだものであってもよい。本発明でいうセメントとは、一般に使用されるポルトランドセメントをいう。また、本発明でいうセメント原料工程とは、石灰石、粘土、珪石、鉄原料等のセメント原料をミル等の粉砕機で粉砕し、プレヒーターで予熱した後に、ロータリーキルン（回転窯）等で焼成する工程を含むものであればよい。この工程の中で、フッ素系樹脂含有物は粉砕を行った後にプレヒーターで予熱した後に、上記のセメント原料と共に、キルンに投入し焼成を行えば、上述のように、セメント原料中のカルシウム化合物とフッ素系樹脂の燃焼で発生したフッ酸が直ちに反応して無害なフッ化カルシウム（ＣａＦ２）となり、そのままセメント原料とすることができる。セメント原料中に投入処理されるフッ素系樹脂の量は、投入量が多いとフッ素系樹脂の燃焼で発生したフッ酸がセメント原料中のカルシウム化合物と反応しきれなくなるので、セメント原料の重量に対して５重量％以下が好ましく、より好ましくは２重量％以下である。また、フッ素系樹脂含有物中に占めるフッ素系樹脂の割合は、フッ素系樹脂の量として上述のように、セメント原料の重量に対して５重量％以下が好ましく、より好ましくは２重量％以下である。 In particular, if the fluororesin has the form of a hollow fiber-like porous membrane, the surface area is increased, so the reaction between hydrofluoric acid generated during combustion of the fluororesin and the calcium compound in the cement raw material Is preferable because it proceeds easily. Furthermore, in order to perform the treatment more safely, a fluorine resin-containing material may be impregnated in advance with a solution containing a calcium compound. Moreover, as a component other than the fluororesin, a plasticizer or an inorganic filler generally used at the time of molding the fluororesin may be included. The cement as used in the field of this invention means the portland cement generally used. The cement raw material process referred to in the present invention is pulverizing cement raw materials such as limestone, clay, silica and iron raw materials with a pulverizer such as a mill, preheating with a pre-heater, and then firing with a rotary kiln (rotary kiln) or the like. What is necessary is just to include a process. In this process, after the fluororesin-containing material is pulverized and then preheated with a preheater, together with the above cement raw material, if it is put into a kiln and fired, as described above, the calcium compound in the cement raw material And hydrofluoric acid generated by the combustion of the fluororesin immediately react to form harmless calcium fluoride (CaF 2 ), which can be used as a cement raw material as it is. The amount of fluororesin charged into the cement raw material will not be able to react with the calcium compound in the cement raw material if the amount of the input is large. Is preferably 5% by weight or less, and more preferably 2% by weight or less. Further, the proportion of the fluorine-based resin in the fluorine-containing resin-containing material is preferably 5% by weight or less, more preferably 2% by weight or less, based on the weight of the cement raw material, as described above, as the amount of the fluorine-based resin. is there.
本発明を実施例に基づいて説明する。
[実施例１]
セメント原料として石灰石を１００ｋｇ、水砕スラグ２９ｋｇ、軟珪石９ｋｇ、鉄原料４ｋｇを合わせて均一に混合し、ミルで粉砕し微粉化したものをプレヒーターに投入し約９００℃に予熱した。ＰＶＤＦを主成分とした樹脂１ｋｇをミルで粉砕した後に同様にプレヒーターに加えて、ロータリーキルンに投入し、微粉炭を燃料としてバーナーで吹き込んで約１４５０℃で焼成を行った。次に、得られた焼成物（クリンカー）を空気冷却し、凝結調整のために少量の石膏を加えて粉砕を行い、セメント原料を作製した。上記製造中にキルンからの排ガスをサンプリングし、排ガス中のフッ化水素ガスの濃度をイオンクロマト法にて測定したところ、１ｐｐｍ未満で非常に低レベルであった。
The present invention will be described based on examples.
[Example 1]
As a cement raw material, 100 kg of limestone, 29 kg of granulated slag, 9 kg of soft silica stone, and 4 kg of iron raw material were mixed together and uniformly mixed, and pulverized and pulverized by a mill were put into a preheater and preheated to about 900 ° C. After 1 kg of resin containing PVDF as a main component was pulverized by a mill, it was similarly added to a preheater and charged into a rotary kiln, and pulverized coal was blown with a burner as a fuel and fired at about 1450 ° C. Next, the obtained fired product (clinker) was air-cooled, a small amount of gypsum was added to adjust the setting, and pulverized to prepare a cement raw material. During the production, the exhaust gas from the kiln was sampled, and the concentration of hydrogen fluoride gas in the exhaust gas was measured by ion chromatography, which was very low at less than 1 ppm.
[実施例２]
セメント原料として石灰石を１００ｋｇ、水砕スラグ２９ｋｇ、軟珪石９ｋｇ、鉄原料４ｋｇを合わせて均一に混合し、ミルで粉砕し微粉化したものをプレヒーターに投入し約９００℃に予熱した。ＰＶＤＦ製の中空糸状多孔質膜０．５ｋｇをミルで粉砕した後に同様にプレヒーターに加えて、ロータリーキルンに投入し、微粉炭を燃料としてバーナーで吹き込んで約１４５０℃で焼成を行った。次に、得られた焼成物（クリンカー）を空気冷却し、凝結調整のために少量の石膏を加えて粉砕を行い、セメント原料を作製した。上記製造中にキルンからの排ガスをサンプリングし、排ガス中のフッ化水素ガスの濃度をイオンクロマト法にて測定したところ、１ｐｐｍ未満で非常に低レベルであった。
[Example 2]
As a cement raw material, 100 kg of limestone, 29 kg of granulated slag, 9 kg of soft silica stone, and 4 kg of iron raw material were mixed together and uniformly mixed, and pulverized and pulverized by a mill were put into a preheater and preheated to about 900 ° C. After pulverizing 0.5 kg of PVDF hollow fiber-like porous membrane with a mill, it was added to a preheater in the same manner and charged into a rotary kiln, and pulverized coal was blown with a burner as fuel, followed by firing at about 1450 ° C. Next, the obtained fired product (clinker) was air-cooled, a small amount of gypsum was added to adjust the setting, and pulverized to prepare a cement raw material. During the production, the exhaust gas from the kiln was sampled, and the concentration of hydrogen fluoride gas in the exhaust gas was measured by ion chromatography, which was very low at less than 1 ppm.
[比較例１]
ＰＶＤＦを主成分とした樹脂１ｋｇを焼却炉で約８００℃で焼却処理した。焼却炉からの排ガスをサンプリングし、排ガス中のフッ素ガスの濃度をイオンクロマト法にて測定したところ、の排ガス中のフッ化水素ガスの濃度を確認したところ１００ｐｐｍ以上で非常に高濃度であった。
[Comparative Example 1]
1 kg of resin mainly composed of PVDF was incinerated at about 800 ° C. in an incinerator. The exhaust gas from the incinerator was sampled, and the concentration of fluorine gas in the exhaust gas was measured by ion chromatography. The concentration of hydrogen fluoride gas in the exhaust gas was confirmed, and it was very high at 100 ppm or more. .
本発明は、フッ素系樹脂含有物の処理分野で好適に利用できる。 The present invention can be suitably used in the field of treatment of fluororesin-containing materials.
Claims (4)
予熱した前記フッ素系樹脂含有物を、プレヒーターで予熱したセメント原料と共にキルン中に投入し燃焼処理することで、前記フッ素系樹脂含有物をセメント原料化することを特徴とするフッ素系樹脂含有物の処理方法。 Crush the fluororesin-containing material and preheat it with a preheater.
The fluorine-based resin-containing material preheated, by charged and be combusted in the kiln together with the preheated cement material in a preheater, a fluorine-based resin-containing product of the fluorine-based resin-containing material, characterized in that raw material for cement Processing method .
前記セメント原料の重量に対して５重量％以下であることを特徴とする請求項１〜３の何れか１項に記載のフッ素系樹脂含有物の処理方法。The method for treating a fluororesin-containing material according to any one of claims 1 to 3, wherein the content is 5% by weight or less based on the weight of the cement raw material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005065400A JP4819376B2 (en) | 2005-03-09 | 2005-03-09 | Treatment method for fluororesin-containing materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005065400A JP4819376B2 (en) | 2005-03-09 | 2005-03-09 | Treatment method for fluororesin-containing materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2006248823A JP2006248823A (en) | 2006-09-21 |
| JP4819376B2 true JP4819376B2 (en) | 2011-11-24 |
Family
ID=37089702
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005065400A Active JP4819376B2 (en) | 2005-03-09 | 2005-03-09 | Treatment method for fluororesin-containing materials |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4819376B2 (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5727954A (en) * | 1980-07-24 | 1982-02-15 | Babcock Hitachi Kk | Cement burning process |
| JPH07247143A (en) * | 1994-03-15 | 1995-09-26 | Sekisui Chem Co Ltd | Production of cement clinker |
| JP4403441B2 (en) * | 1999-11-02 | 2010-01-27 | 住友大阪セメント株式会社 | Cement and manufacturing method thereof |
| JP2003206164A (en) * | 2002-01-11 | 2003-07-22 | Miyoujiyou Cement Kk | Method and apparatus for converting combustible material into fuel |
-
2005
- 2005-03-09 JP JP2005065400A patent/JP4819376B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2006248823A (en) | 2006-09-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4674098B2 (en) | Incineration ash reforming method and incineration ash reforming stoker waste incinerator using the same | |
| JP5440329B2 (en) | Method for producing solidified product from paper sludge incineration ash | |
| CN102775080B (en) | Treatment method of organochlorine pesticide polluted soil | |
| JP4649256B2 (en) | Garbage incinerator with incineration ash reformer | |
| CN103922624A (en) | Clinker sintering system taking carbide slag as calcareous raw material and being used for treating smoke generated in waste incineration | |
| JP4819376B2 (en) | Treatment method for fluororesin-containing materials | |
| AU2014258396B2 (en) | Fluidity improvement type cement clinker | |
| KR101705248B1 (en) | Calcium Chloroaluminate Mineral and Method for Preparing the Same | |
| JP2008273749A (en) | Artificial aggregate and its manufacturing method | |
| CN102807333A (en) | Method for preparing sulphoaluminate cement by using fluorine-containing sludge | |
| JP3224021B2 (en) | Combustion treatment method and combustion treatment device for refuse solid fuel suitable for solidification of combustion ash | |
| JP2017136557A (en) | Method of manufacturing civil engineering material | |
| CN109956691B (en) | Method for treating combustible materials in construction waste | |
| JP4238995B2 (en) | Paper sludge treatment method | |
| JP2009143780A (en) | Cement containing no organic component harmful to cement and method for producing the same | |
| KR20070003374A (en) | Soil solidify composition comprising industrial by-products | |
| KR102246061B1 (en) | Method for manufacturing high purity aluminum oxide and high purity aluminum oxide produced by the method | |
| KR20110091169A (en) | Method for manufactruing cement using fly ash and water sludge | |
| JPH0710618A (en) | Production of cement clinker | |
| CN102476929A (en) | Cement production method using urban refuse as materials | |
| JP2007144411A (en) | Reclamation treatment method in final disposal site | |
| JP7055944B2 (en) | Detoxification method of coal ash | |
| WO2017196942A1 (en) | Sintered ceramics | |
| JP7055943B2 (en) | Detoxification method of coal ash | |
| JP4619193B2 (en) | A method for measuring the hydrogen generation capacity of incineration ash and the like, and an operation control method for the incineration ash reformer by measuring the hydrogen generation capacity. |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20071005 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20100401 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100824 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20101025 |
|
| RD03 | Notification of appointment of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7423 Effective date: 20101025 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20110830 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20110901 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140909 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4819376 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |