JP2006248823A - Method of treating fluororesin-containing material - Google Patents
Method of treating fluororesin-containing material Download PDFInfo
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- JP2006248823A JP2006248823A JP2005065400A JP2005065400A JP2006248823A JP 2006248823 A JP2006248823 A JP 2006248823A JP 2005065400 A JP2005065400 A JP 2005065400A JP 2005065400 A JP2005065400 A JP 2005065400A JP 2006248823 A JP2006248823 A JP 2006248823A
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- Prior art keywords
- fluororesin
- raw material
- cement raw
- containing material
- fluorine
- 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.)
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- 239000000463 material Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000004568 cement Substances 0.000 claims abstract description 29
- 229910052731 fluorine Inorganic materials 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 17
- 229920005989 resin Polymers 0.000 claims description 17
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 16
- 239000011737 fluorine Substances 0.000 claims description 16
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 27
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 19
- 231100001261 hazardous Toxicity 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229940043430 calcium compound Drugs 0.000 description 5
- 150000001674 calcium compounds Chemical class 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 235000019738 Limestone Nutrition 0.000 description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 3
- 238000004255 ion exchange chromatography Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000006028 limestone Substances 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000012510 hollow fiber Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 2
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
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、セメント原料と共にキルン中に投入処理し、セメント原料化することでフッ素系樹脂含有物を処理する方法。
That is, the present invention is as follows.
A method in which a fluorine-containing resin-containing material is treated by pulverizing the fluorine-containing resin-containing material, charging it into a kiln together with a cement material, and converting it into a cement 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. In addition, the cement raw material process referred to in the present invention is pulverized with a pulverizer such as a mill such as limestone, clay, silica, and iron, preheated with a preheater, and then fired in 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 added to a preheater in the same manner, charged into a rotary kiln, and fired at about 1450 ° C. by blowing pulverized coal as a fuel with a burner. 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 porous membrane with a mill, it was similarly put into a preheater, put into a rotary kiln, blown with a burner using pulverized coal 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.
[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.
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Citations (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 |
| JP2001130932A (en) * | 1999-11-02 | 2001-05-15 | Sumitomo Osaka Cement Co Ltd | Cement and method for producing the same |
| 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
Patent Citations (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 |
| JP2001130932A (en) * | 1999-11-02 | 2001-05-15 | Sumitomo Osaka Cement Co Ltd | Cement and method for producing the same |
| JP2003206164A (en) * | 2002-01-11 | 2003-07-22 | Miyoujiyou Cement Kk | Method and apparatus for converting combustible material into fuel |
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