JP4238995B2 - Paper sludge treatment method - Google Patents
Paper sludge treatment method Download PDFInfo
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- JP4238995B2 JP4238995B2 JP2004044806A JP2004044806A JP4238995B2 JP 4238995 B2 JP4238995 B2 JP 4238995B2 JP 2004044806 A JP2004044806 A JP 2004044806A JP 2004044806 A JP2004044806 A JP 2004044806A JP 4238995 B2 JP4238995 B2 JP 4238995B2
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- paper sludge
- lime
- ash
- incineration
- fluorine
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- 239000010802 sludge Substances 0.000 title claims description 46
- 238000000034 method Methods 0.000 title claims description 19
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 36
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 36
- 239000004571 lime Substances 0.000 claims description 36
- 238000007670 refining Methods 0.000 claims description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 14
- 239000011737 fluorine Substances 0.000 claims description 14
- 229910052731 fluorine Inorganic materials 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000003440 toxic substance Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 6
- 238000010828 elution Methods 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 239000010436 fluorite Substances 0.000 claims description 4
- 231100000167 toxic agent Toxicity 0.000 claims description 2
- 239000002699 waste material Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 5
- 231100000614 poison Toxicity 0.000 description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 4
- 239000000809 air pollutant Substances 0.000 description 3
- 231100001243 air pollutant Toxicity 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003405 preventing effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/40—Valorisation of by-products of wastewater, sewage or sludge processing
Description
本発明は、製紙過程で廃棄物として発生するペーパースラッジを処分あるいは有効利用することを目的とするペーパースラッジの処理方法に関する。 The present invention relates to a paper sludge treatment method for the purpose of disposing or effectively using paper sludge generated as waste in the papermaking process.
周知のように、この種のペーパースラッジ（製紙スラッジ）は焼却されてその焼却灰を埋立処分することが通常であるが、たとえば特許文献１に示されるように焼却灰を地盤改良材として有効利用することも検討されている。
しかし、ペーパースラッジには各種の有害物質が含まれており、特に古紙の再生過程で発生するペーパースラッジにはフッ素が含まれているので、それをそのまま焼却して焼却灰をそのまま埋立処分することは環境保全の観点から好ましくなく、特にフッ素については環境基準に適合しないためにそのままでは処分できない場合も多い。また、焼却灰の有効利用を図るためには有害物質の溶出を防止するための処理を行うことが不可欠であるが、特にフッ素の溶出量を効果的に低減させるための有効適切な処理手法は確立されておらず、その開発が急務とされている。 However, paper sludge contains various harmful substances, especially paper sludge generated in the recycling process of waste paper contains fluorine, so incinerate it as it is and incinerate ash as landfill. Is not preferable from the viewpoint of environmental conservation, and in particular, fluorine cannot be disposed as it is because it does not conform to environmental standards. In addition, in order to effectively use incinerated ash, it is indispensable to carry out treatment to prevent the leaching of harmful substances, but in particular, an effective and appropriate treatment method to effectively reduce the amount of fluorine leached It has not been established and its development is urgently needed.
上記事情に鑑み、請求項１の発明は、ペーパースラッジを処分あるいは有効利用することを目的として処理するための方法であって、処理対象のペーパースラッジに石灰精製残滓を混合し、その混合物を焼却することによって石灰精製残滓に含まれている石灰成分を排気ガス中のＳＯxと反応させることによりＳＯxの排出を低減させ、かつ、焼却時に石灰成分を生成させてその石灰成分をペーパースラッジ焼却灰に含有させるとともに、石灰成分を含有させたペーパースラッジ焼却灰に水を加えることによって、ペーパースラッジ焼却灰中のカルシウムとフッ素とを反応させてホタル石を生成させてフッ素の溶出を低減させることを特徴とする。 In view of the above circumstances, the invention of claim 1 is a method for treating paper sludge for the purpose of disposal or effective use, mixing lime refining residue with paper sludge to be treated, and incinerating the mixture The lime component contained in the lime refining residue is reacted with SOx in the exhaust gas to reduce SOx emission, and at the time of incineration, the lime component is generated and the lime component is converted into paper sludge incineration ash. In addition to containing lime component, water is added to the paper sludge incineration ash to cause calcium and fluorine to react with the paper sludge incineration ash to produce fluorite to reduce fluorine elution. And
請求項２の発明は、上記の処理方法において、さらにペーパースラッジ焼却灰に固化材を加えることによって、ペーパースラッジ焼却灰中の有害物質を不溶化することを特徴とする。 The invention of claim 2 is characterized in that, in the above processing method, a toxic substance in the paper sludge incinerated ash is insolubilized by adding a solidifying material to the paper sludge incinerated ash.
請求項１の発明によれば、ペーパースラッジを焼却するに際して同じく廃棄物である石灰精製残滓（石灰スラッジ）を混合してその混合物を焼却することにより、石灰精製残滓に含まれている酸化カルシウム（ＣａＯ）等の石灰成分がペーパースラッジに含まれているフッ素等の有害重金属と反応して有害物質が自ずと安定化され、焼却灰中の残留有害物が低減してそのまま支障なく処分することが可能な程度の無害化を実現することができる。しかも、カルシウム成分は排気ガス中の有害成分であるＳＯｘとも反応するので、排気ガス中の大気汚染物質を低減して大気汚染防止効果も得られる。また、そのような混合物を焼却して得られるペーパースラッジ焼却灰は自ずと石灰成分を多く含有するものとなり、これは自ずと優れた不良土改良効果を有するものとなるので、これをそのまま地盤改良材として有効に利用することが可能となる。 According to the invention of claim 1, when paper sludge is incinerated, lime refining residue (lime sludge), which is also waste, is mixed and the mixture is incinerated, so that calcium oxide contained in the lime refining residue ( Lime components such as CaO) react with toxic heavy metals such as fluorine contained in the paper sludge and the toxic substances are naturally stabilized, and the residual toxic substances in the incineration ash are reduced and can be disposed of without any problems. A certain degree of detoxification can be realized. In addition, since the calcium component also reacts with SOx, which is a harmful component in the exhaust gas, the air pollutant in the exhaust gas can be reduced and an air pollution preventing effect can be obtained. In addition, paper sludge incineration ash obtained by incineration of such a mixture will naturally contain a lot of lime components, and this will naturally have an excellent effect of improving bad soil, so this can be used as a ground improvement material as it is. It can be used effectively.
すなわち、本発明によれば、ペーパースラッジ焼却灰中の有害物質の含有量やその溶出量を有効に低減できることはもとより、ペーパースラッジのみならず同じく廃棄物として処分されていた石灰精製残滓も資源として有効にリサイクルすることを可能とするものである。しかも、本発明の処理方法はペーパースラッジと石灰精製残滓とを単に混合して焼却するだけであるから、従来のペーパースラッジの焼却設備とその工程をそのまま採用可能であり、したがってその処理のために格別の設備を必要としないし、さしたる処理コストも必要とせず、また大量処理や連続処理も可能であるし、焼却の際に発生する排気ガス中の有害成分であるＳＯｘも低減させ得るものであるから、ペーパースラッジおよび石灰精製残滓の処理手法として、またそれらの廃棄物を利用した地盤改良材の製造手法として、極めて有効である。 That is, according to the present invention, not only can the content of toxic substances in paper sludge incineration ash and its elution amount be effectively reduced, but also lime refining residue that has been disposed of as waste as well as paper sludge is used as a resource. It can be effectively recycled. Moreover, since the treatment method of the present invention is simply mixing and incinerating the paper sludge and the lime refining residue, the conventional paper sludge incineration equipment and its process can be employed as it is, and therefore for the treatment. No special equipment is required, no significant processing costs are required, mass processing and continuous processing are possible, and SOx, which is a harmful component in exhaust gas generated during incineration, can be reduced. because there, as the processing technique of paper sludge and lime purification residue, also as a manufacturing method of ground improvement material utilizing their waste it is extremely effective.
そのうえ、上記に加えて焼却灰にさらに水を加えることにより、僅かに残留するフッ素が石灰成分との水和反応を生じることによって安定なホタル石（ＣａＦ２）が生成され、それによりフッ素の溶出量をさらに抑制することができる。 Moreover, by adding water to the incinerated ash in addition to the above, a slight amount of fluorine causes a hydration reaction with the lime component, thereby generating stable fluorite (CaF2), whereby the amount of fluorine eluted Can be further suppressed.
さらに、請求項２の発明によれば、焼却灰に固化材を混合して固化させることにより、残留有害物が固化されて不溶化され、その溶出量をより一層低減させることができる。 Furthermore, according to the invention of claim 2 , by mixing the solidified material with the incinerated ash and solidifying, the residual harmful substances are solidified and insolubilized, and the amount of elution can be further reduced.
図１に本発明の基本工程を示す。これは処理対象のペーパースラッジに石灰精製残滓を混合し、その混合物を焼却することを主眼とする。 FIG. 1 shows the basic steps of the present invention . The main purpose of this is to mix lime refining residue with the paper sludge to be treated and incinerate the mixture.
石灰精製残滓は、たとえば紙製品のコーティング材等として利用される炭酸カルシウム微粉末の製造工程において発生するもので、その主成分は水酸化カルシウムであるが、従来においては有効利用されることなく単に廃棄物として埋立処分されているものである。 The lime refining residue is produced in the production process of calcium carbonate fine powder used as, for example, a coating material for paper products, and the main component thereof is calcium hydroxide. It is landfilled as waste.
ペーパースラッジに対する石灰精製残滓の混合量は適宜設定すれば良いが、後述するように焼却により生成されるペーパースラッジ焼却灰（以下、ＰＳ灰）に含有される石灰成分（ＣａＯ）が２０〜３０％程度となるように混合量を調整すると良く、たとえばペーパースラッジ１ｔｏｎ当たりの混合量を５０Ｋｇ程度とすることが良い。 What is necessary is just to set suitably the mixing amount of the lime refinement | purification residue with respect to paper sludge, but the lime component (CaO) contained in the paper sludge incineration ash (henceforth PS ash) produced | generated by incineration is 20-30% so that it may mention later. For example, the mixing amount per 1 ton of paper sludge is preferably about 50 kg.
なお、上記の混合物の焼却は流動床式の焼却設備等による従来のペーパースラッジ焼却工程によりそのまま実施可能である。また、混合物の焼却に際しては各種の大気汚染物質低減材たとえばドロマイト等を添加することも好ましい。 The incineration of the mixture can be carried out as it is by a conventional paper sludge incineration process using a fluidized bed type incineration facility or the like. It is also preferable to add various air pollutant reducing materials such as dolomite when the mixture is incinerated.
上記のように、ペーパースラッジに石灰精製残滓を混合してその混合物を焼却することにより、石灰精製残滓中に含まれる石灰成分である酸化カルシウム（ＣａＯ）とペーパースラッジに含まれる有害重金属特にフッ素とが反応し、それにより有害物質が自ずと安定化されてＰＳ灰中の残留有害物を自ずと低減させることができる。また、石灰精製残滓中のカルシウム成分は排気ガス中の有害成分であるＳＯｘとも反応するので、排気ガス中の大気汚染物質を低減して大気汚染防止効果も得られる。 As described above, by mixing lime refining residue with paper sludge and incinerating the mixture, calcium oxide (CaO), which is a lime component contained in the lime refining residue, and harmful heavy metals, particularly fluorine, contained in the paper sludge Reacts, whereby the harmful substances are naturally stabilized and the residual harmful substances in the PS ash can be reduced naturally. Further, since the calcium component in the lime refining residue also reacts with SOx, which is a harmful component in the exhaust gas, the air pollutant in the exhaust gas can be reduced and the air pollution preventing effect can be obtained.
したがって上記のＰＳ灰はそのまま埋立等の処分をすることが可能な程度に無害化されるが、そのＰＳ灰には適量のシリカやアルミナ、酸化鉄等の細粒成分を含み、かつ上記のように石灰精製残滓との混合焼却により自ずと石灰成分を含有するものとなっており、特にＰＳ灰中のＣａＯの含有量が２０〜３０％程度ないしそれ以上となるように調製することにより、このＰＳ灰は自ずと優れた不良土改良効果を有するものとなるから、これをそのまま地盤改良材として、あるいは地盤改良材の原料として有効に利用することも可能となる。 Therefore, the PS ash is rendered harmless to such an extent that it can be disposed of as landfill, but the PS ash contains an appropriate amount of fine-grained components such as silica, alumina, iron oxide and the like. The lime component is naturally contained by mixed incineration with lime refining residue, and this PS is especially prepared by adjusting the content of CaO in PS ash to about 20 to 30% or more. Since ash naturally has an excellent effect of improving poor soil, it can be effectively used as it is as a ground improvement material or as a raw material for a ground improvement material.
すなわち、本処理方法によれば、ＰＳ灰中の残留有害物を低減でき、したがってそれからの有害物の溶出量も自ずと低減できることはもとより、従来においてはいずれも廃棄物として処分されていたペーパースラッジと石灰精製残滓の双方を資源として有効にリサイクルできることになる。しかも、ペーパースラッジと石灰精製残滓とを単に混合して焼却するという工程によるだけであるから、その処理のために格別の設備やさしたる処理コストを要せず、また大量処理も可能であり、ペーパースラッジおよび石灰精製残滓を無害化し有効活用するための処理手法として、またそれらの廃棄物を利用した地盤改良材ないしその原料の製造手法として、極めて有効である。 That is, according to this treatment method, residual toxic substances in PS ash can be reduced, and thus the amount of toxic substances leached from the ash can be reduced naturally, as well as paper sludge that has been disposed of as waste in the past. Both lime refining residues can be effectively recycled as resources. Moreover, because it is simply a process of mixing and incinerating paper sludge and lime refining residue, no special equipment or processing costs are required for the processing, and a large amount of processing is possible. It is extremely effective as a treatment technique for detoxifying sludge and lime refining residue and effectively utilizing them, and as a technique for producing ground improvement materials or raw materials using these wastes.
図２は本発明の実施形態を示す。これは、上記の基本工程による処理により得たＰＳ灰をそのまま処分ないし利用するのではなく、さらに水を加えてその含水率をたとえば２０〜３０％程度とし、それを所定期間（たとえば７日程度）静置して養生した後、さらにセメント等の固化材をたとえば２〜３％程度混合（その際、必要に応じて適量の水を添加して湿潤状態とすれば良い）するようにしたものである。これによれば、ＰＳ灰中に僅かに残留するフッ素と石灰成分との水和反応により安定なホタル石（ＣａＦ２）が生成されるのでフッ素の溶出量をより確実に抑制でき、また各種の残留有害物が固化材により固化されて不溶化されることによりその溶出量をより一層低減させることができる。 FIG. 2 shows an embodiment of the present invention . This is not to dispose or use the PS ash obtained by the above basic process as it is, but to add water to make the water content about 20-30%, for example, for a predetermined period (for example, about 7 days). ) After standing and curing, further solidified material such as cement is mixed, for example, about 2-3% (in that case, an appropriate amount of water may be added to make it wet) It is. According to this, since stable fluorite (CaF2) is produced by the hydration reaction between fluorine and lime components slightly remaining in PS ash, the amount of fluorine eluted can be more reliably suppressed, and various residuals can be obtained. Since harmful substances are solidified and insolubilized by a solidifying material, the amount of elution can be further reduced.
実験例によれば、上記のようにペーパースラッジに石灰精製残滓を混合して焼却して得たＰＳ灰に対し、さらに加水による水和反応処理と固化材添加による不溶化処理を行うことにより、ペーパースラッジを何等の処理を行うことなく単に焼却した場合に比較してフッ素の溶出量を５％以下にまで低減させることが確認され、本発明の有効性が実証されている。 According to the experimental example, the PS ash obtained by mixing and incinerating the lime refining residue into the paper sludge as described above is further subjected to hydration reaction treatment by addition of water and insolubilization treatment by addition of a solidifying material. Compared to the case where the sludge is simply incinerated without any treatment, it was confirmed that the amount of fluorine elution was reduced to 5% or less, and the effectiveness of the present invention was proved.
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| JP2004044806A JP4238995B2 (en) | 2004-02-20 | 2004-02-20 | Paper sludge treatment method |
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| JP4552111B2 (en) * | 2004-02-20 | 2010-09-29 | 清水建設株式会社 | Manufacturing method of ground material |
| JP4957371B2 (en) * | 2007-05-11 | 2012-06-20 | 王子製紙株式会社 | Method for removing sulfur in fluidized bed combustor |
| JP2009195791A (en) * | 2008-02-20 | 2009-09-03 | Oji Paper Co Ltd | Treatment method of incineration ash |
| KR101541410B1 (en) * | 2014-05-23 | 2015-08-04 | 한국기계연구원 | System and method for processing sludge and used refrigerant |
| KR101581824B1 (en) * | 2014-05-23 | 2016-01-04 | 한국기계연구원 | System and method for processing used refrigerant using Calcium-containing sludge |
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