JP2014198301A - Method of treating combustion ash - Google Patents
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- JP2014198301A JP2014198301A JP2013074729A JP2013074729A JP2014198301A JP 2014198301 A JP2014198301 A JP 2014198301A JP 2013074729 A JP2013074729 A JP 2013074729A JP 2013074729 A JP2013074729 A JP 2013074729A JP 2014198301 A JP2014198301 A JP 2014198301A
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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
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/78—Recycling of wood or furniture waste
Abstract
Description
本発明は、燃焼灰を処理する方法に関する。特に本発明の処理方法を適用することにより、フッ素や六価クロム等の無機有害成分が燃焼灰から溶出することを抑制できる。また、本発明によれば、被処理物である燃焼灰の吸水性が維持された処理物が得られるため、処理物を高い吸水性を持つ吸水材などとして利用できる。 The present invention relates to a method for treating combustion ash. In particular, by applying the treatment method of the present invention, it is possible to prevent inorganic harmful components such as fluorine and hexavalent chromium from eluting from the combustion ash. In addition, according to the present invention, a treated product is obtained in which the water absorption of the combustion ash that is the object to be treated is maintained.
近年、環境保全の観点から、産業廃棄物の削減が強く求められている。産業廃棄物の削減は、発電や廃棄物焼却等を行っている全ての企業及び自治体に対する要請であり、紙・パルプ業界もその例外ではない。 In recent years, reduction of industrial waste has been strongly demanded from the viewpoint of environmental conservation. The reduction of industrial waste is a request to all companies and local governments that are engaged in power generation and waste incineration, and the paper and pulp industry is no exception.
このような状況の中、燃焼灰の取り扱いが大きな社会問題となっている。現在、燃焼灰は、その一部が、セメント原料や製鉄用酸化防止剤、混和剤などの再生材料として有効利用されているが、残りは産業廃棄物として埋め立てられることが多い。再利用があまり進んでいない原因として、燃焼灰は土壌汚染対策法施行規則（平成十四年環境省令第二十九号）第五条第三項第四号の規定に基づき定められた土壌環境基準（環境省告示第十八号、改正環境省告示第四十八号）に挙げられている有害成分の溶出量が基準値を超過することが多いことがある。上記有害成分のうち、有機物有害成分は焼却時に分解されるため、焼却灰ではほとんどの場合問題とはならないが、フッ素、ほう素、六価クロム、鉛をはじめとする無機物有害成分の溶出量は基準を超過することが多い。有害成分溶出量が土壌環境基準値を超過している場合、その燃焼灰は土壌に施用することができず、再利用を図る上で大きな障壁となっている。 Under such circumstances, handling of combustion ash is a big social problem. Currently, a part of the combustion ash is effectively used as a recycled material such as a cement raw material, an iron-making antioxidant and an admixture, but the rest is often landfilled as industrial waste. Combustion ash is one of the reasons for not reusing the soil environment in accordance with the provisions of Article 5, Paragraph 4, Item 4 of the Ordinance for Enforcement of the Soil Contamination Countermeasures Law (Ministry of Environment Ordinance No. 29, 2004). In many cases, the elution amount of harmful components listed in the standards (Ministry of the Environment Notification No. 18 and Amended Ministry of the Environment Notification No. 48) exceeds the standard value. Of the above harmful components, organic harmful components are decomposed during incineration, so incineration ash is not a problem in most cases, but the elution amount of inorganic harmful components such as fluorine, boron, hexavalent chromium and lead is Often the standard is exceeded. If the leaching amount of harmful components exceeds the soil environment standard value, the combustion ash cannot be applied to the soil, which is a big barrier to reuse.
また、ほとんどの場合、燃焼灰は細かい固体状の粉末であり、取り扱う上で粉塵としての注意も要する。排出や輸送を行う際に、粉塵飛散防止を図るため焼却灰に水分を添加することが一般に行われているが、水分を添加した燃焼灰を大気中に放置しておくと、添加された水分が焼却灰中のカルシウム分と反応して水酸化カルシウムが形成され、この水酸化カルシウムが大気中の二酸化炭素と反応することにより炭酸カルシウムとなるため、焼却灰の溶出ｐＨが低下し、結果として六価クロムの溶出量が増大する。 Further, in most cases, the combustion ash is a fine solid powder and requires attention as dust when handled. When discharging or transporting, it is common to add moisture to the incineration ash to prevent dust scattering, but if the combustion ash with added moisture is left in the atmosphere, the added moisture Reacts with the calcium content in the incineration ash to form calcium hydroxide, and this calcium hydroxide reacts with carbon dioxide in the atmosphere to form calcium carbonate, which lowers the elution pH of the incineration ash, resulting in The elution amount of hexavalent chromium increases.
土壌汚染対策法に規定される土壌環境基準を満足すべく、被汚染物に何らかの処理剤を添加して有害成分溶出量の低下を図る技術は、これまでに数多く検討されている。特許文献１には、６価クロム汚染土壌をポリフェノールおよびリン酸またはリン酸塩と接触させることによる、汚染土壌の処理方法が開示されている。また、特許文献２には、有機塩素化合物により汚染され、重金属類を含む汚染物に、酸化剤として過流酸塩を添加した後に還元剤を添加することを特徴とする化学物質による汚染の浄化方法が開示されている。特許文献３には、燃焼灰にジチオカルバミン酸、澱粉、非晶質珪素化合物を添加することにより、鉛の溶出を抑制する方法が開示されている。 In order to satisfy the soil environmental standards stipulated in the Soil Contamination Countermeasures Law, a number of techniques for reducing the amount of harmful components eluted by adding some treatment agent to contaminated materials have been studied so far. Patent Document 1 discloses a method for treating contaminated soil by bringing hexavalent chromium-contaminated soil into contact with polyphenol and phosphoric acid or phosphate. Further, Patent Document 2 discloses purification of contamination by a chemical substance characterized by adding a reducing agent after adding a persulfate as an oxidizing agent to a contaminant containing an organic chlorine compound and containing heavy metals. A method is disclosed. Patent Document 3 discloses a method for suppressing elution of lead by adding dithiocarbamic acid, starch, and an amorphous silicon compound to combustion ash.
本発明の主たる課題は、有害物質を含む廃棄物、特に燃焼灰を有効かつ簡便に処理する方法を提供することである。特に、燃焼灰に含まれるフッ素や六価クロム等の無機有害成分の溶出量を低減し、かつ同時に被処理物の吸水性を損なわないように処理を行うことによって、処理物を高い吸水性を持つ吸水性材料などとしても利用できるような、付加価値のある処理物を得ることも目的とする。 The main subject of this invention is providing the method of processing the waste containing a hazardous | toxic substance, especially combustion ash effectively and simply. In particular, by reducing the elution amount of inorganic harmful components such as fluorine and hexavalent chromium contained in combustion ash, and at the same time, processing so as not to impair the water absorption of the processed material, Another object is to obtain a processed product with added value that can be used as a water-absorbing material.
本発明によって、燃焼灰を有効かつ簡便に処理する方法が提供される。また、本発明の処理方法によれば、燃焼灰を原料として、吸水材などとして有用な処理物を得ることができる。 By this invention, the method of processing combustion ash effectively and simply is provided. Further, according to the treatment method of the present invention, it is possible to obtain a treated product useful as a water absorbing material or the like using combustion ash as a raw material.
具体的には、本発明によって、燃焼灰１００質量部に対して、二水石膏、硫酸金属塩または無機リン酸から選択される１種以上と、ジエチルジチオカルバミン酸塩を０．３〜３質量部、と水とを添加し、混練して処理物を得ることを含む、燃焼灰の処理方法が提供される。 Specifically, according to the present invention, 0.3 to 3 parts by mass of one or more selected from dihydrate gypsum, sulfate metal salt or inorganic phosphoric acid and diethyldithiocarbamate with respect to 100 parts by mass of combustion ash. , And water are added and kneaded to obtain a treated product.
本発明により、有害物質を含む廃棄物である燃焼灰を効率的かつ簡便に処理する方法が提供される。特に本発明によれば、燃焼灰に含まれるフッ素や六価クロム等の無機有害成分の溶出を抑制し、かつ同時に焼却灰の飛散防止を図ることもできる。また、本発明によれば、土壌改良材、吸水性材料などとしても利用できるような付加価値のある処理物を、燃焼灰を原料として製造することができる。本発明においては、特別な装置または機器を必要とせず、薬品を添加するのみの比較的シンプルな工程で、燃焼灰の処理を完結させることができる。 The present invention provides a method for efficiently and simply treating combustion ash, which is a waste containing hazardous substances. In particular, according to the present invention, elution of inorganic harmful components such as fluorine and hexavalent chromium contained in combustion ash can be suppressed, and at the same time, incineration ash can be prevented from scattering. Moreover, according to this invention, the processed material with added value which can be utilized also as a soil improvement material, a water absorbing material, etc. can be manufactured by using combustion ash as a raw material. In the present invention, the treatment of the combustion ash can be completed by a relatively simple process in which only a chemical is added without requiring a special device or equipment.
以下、本発明について詳細を記載する。本発明においては、燃焼灰１００重量部に対して、二水石膏、硫酸金属塩または無機リン酸から選択される１種以上と、ジエチルジチオカルバミン酸塩を０．１〜３質量部、及び水を添加し、混練して処理物を得る。 Hereinafter, the present invention will be described in detail. In the present invention, with respect to 100 parts by weight of combustion ash, at least one selected from dihydrate gypsum, sulfate metal salt or inorganic phosphoric acid, 0.1 to 3 parts by mass of diethyldithiocarbamate, and water. Add and knead to obtain a processed product.
本発明において「燃焼灰」は、原料に対して高温で熱処理を施した後に残る灰（固形分）を意味する。燃焼灰の原料は特に制限されないが、製紙スラッジ、石炭、紙を含む廃棄物、バイオマス燃料、木屑、ＲＰＦ（産業系廃プラスチック・古紙類固形燃料）、廃タイヤ、汚泥燃料、複合燃料からなる群より選択される少なくとも１種を含んでなる原料を使用することができる。本発明においては、上記の灰の原料のうち、製紙スラッジおよび／または紙を含む廃棄物および／またはバイオマス燃料を原料とする燃焼灰を使用することが好ましく、製紙スラッジおよび／またはバイオマス燃料を原料とする燃焼灰を使用することがより好ましく、製紙スラッジを原料とする燃焼灰を使用することが特に好ましい。 In the present invention, “burning ash” means ash (solid content) remaining after heat treatment of a raw material at a high temperature. The raw material of the combustion ash is not particularly limited, but it is a group consisting of paper sludge, coal, paper-containing waste, biomass fuel, wood waste, RPF (industrial waste plastic and waste paper solid fuel), waste tire, sludge fuel, and composite fuel. A raw material comprising at least one selected from the above can be used. In the present invention, among the above ash raw materials, it is preferable to use paper sludge and / or paper-containing waste and / or combustion ash made from biomass fuel, and paper sludge and / or biomass fuel are used as raw materials. It is more preferable to use the combustion ash as described above, and it is particularly preferable to use the combustion ash made from papermaking sludge.
本発明においては、上記原料に加えて助燃材を併用して燃焼灰を得ることができ、例えば重油、灯油、石油、石炭、天然ガス、液化天然ガス、液化石油ガス、都市ガス、パルプ工程廃液などの、当技術分野で周知の燃料を加えてもよい。 In the present invention, combustion ash can be obtained by using an auxiliary combustor in addition to the above raw materials, such as heavy oil, kerosene, petroleum, coal, natural gas, liquefied natural gas, liquefied petroleum gas, city gas, and pulp process waste liquid. Fuels well known in the art may be added.
上記原料に対して熱処理を施す熱処理工程は、当該技術分野で周知のあらゆる燃焼装置を使用して行うことができる。燃焼装置の形式、大きさなども特に制限されないが、例えば、焼却炉、ボイラーなどを好適に挙げることができ、流動床式の燃焼装置が好ましい。 The heat treatment process for heat-treating the raw material can be performed using any combustion apparatus known in the art. The type and size of the combustion apparatus are not particularly limited, and for example, an incinerator, a boiler and the like can be preferably cited, and a fluidized bed combustion apparatus is preferable.
上記の熱処理を施す際の温度は当業者が任意に決めることができ、５００〜１５００℃の範囲が好ましく、６００〜１２００℃の範囲がより好ましく、７００〜１０００℃の範囲が最も好ましい。また、上記熱処理の時間も適宜選択することができ、燃焼装置における原料の平均滞留時間は、１時間以内が好ましく、３〜３０分間以内がより好ましく、１０分間以内がさらに好ましい。 The temperature at the time of performing the above heat treatment can be arbitrarily determined by those skilled in the art, preferably in the range of 500 to 1500 ° C, more preferably in the range of 600 to 1200 ° C, and most preferably in the range of 700 to 1000 ° C. The heat treatment time can also be appropriately selected, and the average residence time of the raw material in the combustion apparatus is preferably within 1 hour, more preferably within 3 to 30 minutes, and even more preferably within 10 minutes.
このようにして得られた燃焼灰に対し、本発明の処理方法では、特定量の水と薬品を添加する。本発明においては、添加前に、燃焼灰に何らかの処理を行うこともできる。例えば、本発明の目的を損なわない範囲において、粉砕、破砕、解砕、分級、再燃焼、再乾燥、磁力選別などの前処理を、当業者に周知のあらゆる適切な装置を用いて、燃焼灰に対して行うこともできる。別法として、熱処理された燃焼灰に何らかの前処理を行わずに、そのまま本発明に利用することもでき、消費エネルギー及びコストの観点から、前処理を行わないことが好ましい。 In the treatment method of the present invention, specific amounts of water and chemicals are added to the combustion ash thus obtained. In the present invention, the combustion ash can be subjected to some treatment before addition. For example, as long as the object of the present invention is not impaired, pretreatment such as grinding, crushing, crushing, classification, reburning, redrying, magnetic sorting, etc. is performed using any suitable apparatus known to those skilled in the art. Can also be done. Alternatively, the heat-treated combustion ash can be used in the present invention as it is without any pretreatment, and it is preferable not to perform the pretreatment from the viewpoint of energy consumption and cost.
本発明では、燃焼灰１００質量部に対して、ジエチルジチオカルバミン酸塩を０．３〜３質量部添加することが必要であり、０．５〜２質量部が好ましく、０．５〜１質量部がさらに好ましい。ジエチルジチオカルバミン酸塩の添加量が少なすぎると、無機有害成分溶出量を低減させる効果が十分に発揮されない。また、ジエチルジチオカルバミン酸塩の添加量を過剰にすることは、主に費用の点から、工業的に現実的な方法ではない。ジエチルジチオカルバミン酸塩としては、ジエチルジチオカルバミン酸カリウム、ジエチルジチオカルバミン酸ナトリウム、ジエチルジチオカルバミン酸アンモニウム等が挙げられ、ジエチルジチオカルバミン酸カリウム（Ｋ（Ｃ２Ｈ５）２ＮＣＳＳ）が好ましい。 In this invention, it is necessary to add 0.3-3 mass parts of diethyl dithiocarbamate with respect to 100 mass parts of combustion ash, 0.5-2 mass parts is preferable, 0.5-1 mass part Is more preferable. If the amount of diethyldithiocarbamate added is too small, the effect of reducing the elution amount of inorganic harmful components is not sufficiently exhibited. Further, excessive addition of diethyldithiocarbamate is not an industrially practical method mainly from the viewpoint of cost. Examples of the diethyldithiocarbamate include potassium diethyldithiocarbamate, sodium diethyldithiocarbamate, ammonium diethyldithiocarbamate and the like, and potassium diethyldithiocarbamate (K (C 2 H 5 ) 2 NCSS) is preferable.
本発明では、さらに特定の処理剤を燃焼灰に添加する。本発明において「処理剤」とは、燃焼灰に添加することによって、主として燃焼灰に含まれるフッ素や六価クロム等の無機有害成分の溶出量を低減させる効果を有する薬品を指す。具体的には、二水石膏、硫酸金属塩、無機リン酸から選択される１種以上の処理剤を本発明において使用する。硫酸金属塩としては任意の硫酸金属塩を使用することができるが、鉄を含有する硫酸金属塩が好ましく、硫酸第一鉄が特に好ましい。また、無機リン酸としては正リン酸を使用することが好ましい。 In the present invention, a specific treatment agent is further added to the combustion ash. In the present invention, the “treating agent” refers to a chemical having an effect of reducing the amount of elution of inorganic harmful components such as fluorine and hexavalent chromium contained in the combustion ash by adding to the combustion ash. Specifically, at least one treatment agent selected from dihydrate gypsum, metal sulfate, and inorganic phosphoric acid is used in the present invention. Although any metal sulfate can be used as the metal sulfate, a metal sulfate containing iron is preferable, and ferrous sulfate is particularly preferable. Moreover, it is preferable to use orthophosphoric acid as inorganic phosphoric acid.
本発明の特徴の１つは、上記の処理剤の添加量を燃焼灰１００質量部に対して１〜１０質量部とすることであり、３〜７重量部が好ましく、５〜７質量部がさらに好ましい。処理剤の添加量が少なすぎると、無機有害成分溶出量を低減させる効果が十分に発揮されない。また、処理剤の添加量を過剰に多くすることは、主に費用の点から、工業的に現実的な方法ではない。 One of the features of the present invention is that the amount of the treatment agent added is 1 to 10 parts by mass with respect to 100 parts by mass of combustion ash, preferably 3 to 7 parts by weight, and 5 to 7 parts by mass. Further preferred. When there is too little addition amount of a processing agent, the effect of reducing the amount of inorganic harmful component elution is not fully exhibited. Further, excessively adding the treatment agent is not an industrially practical method mainly from the viewpoint of cost.
本発明においては、燃焼灰に対して、上記処理剤の他に水も添加される。処理剤は、予め水に加えて水溶液または懸濁液とし、これを燃焼灰に添加することもできる。この場合、処理剤を水分と混合させる方法は当業者に周知のあらゆる方法を使用することができ、一例として撹拌機、混合機、ホモミキサー、スターラー、アジテーターなどが挙げられるが、これらに限定されるものではない。また、これらの薬品は予め水に加えずに、燃焼灰に水が添加される前または後に、水とは別に灰に添加されるようにすることもできる。 In the present invention, water is also added to the combustion ash in addition to the treatment agent. The treating agent can be added in advance to water to form an aqueous solution or suspension, which can be added to the combustion ash. In this case, any method known to those skilled in the art can be used as a method for mixing the treatment agent with moisture, and examples thereof include a stirrer, a mixer, a homomixer, a stirrer, an agitator, and the like, but are not limited thereto. It is not something. Further, these chemicals may be added to the ash separately from water before or after the water is added to the combustion ash without being added to the water in advance.
本発明では燃焼灰に対して特定量の水を添加するが、水としては、例えば、純水、蒸留水、水道水、工業用水、雨水、地下水等の比較的不純物が少ない水、および、何らかの物質が含有されてなる溶液、水性懸濁液、水性スラリーが含まれる。本発明においては、水によって燃焼灰の飛散が防止され、また、水を添加して後述する混練処理を行うことによって有害成分の溶出が効率的に抑制される。 In the present invention, a specific amount of water is added to the combustion ash. As the water, for example, pure water, distilled water, tap water, industrial water, rainwater, groundwater, and the like, and water with relatively few impurities, A solution containing the substance, an aqueous suspension, and an aqueous slurry are included. In the present invention, scattering of combustion ash is prevented by water, and elution of harmful components is efficiently suppressed by adding water and performing a kneading process described later.
燃焼灰に水を添加する工程は、当技術分野で周知のあらゆる水分添加装置を用いて行うことができる。水添加装置の例として、撹拌機、混合機、混練機、一軸混練機、二軸混練機、造粒機、ミキサーなどが挙げられるが、燃焼灰と水分がある程度均一に混合されればよく、適当な装置はこれらに限られるものではない。 The step of adding water to the combustion ash can be performed using any water addition device known in the art. Examples of the water addition device include a stirrer, a mixer, a kneader, a uniaxial kneader, a biaxial kneader, a granulator, a mixer, etc., as long as the combustion ash and moisture are mixed to some extent, Suitable devices are not limited to these.
水を添加する際に、上記の添加装置をはじめとする添加装置を運転する条件は、それぞれの装置に応じて任意に定めることができる。制御可能な運転条件としては、回転速度、燃焼灰の投入速度およびタイミング、水の投入速度及びタイミング、水の添加方法、運転時間が挙げられる。当業者であれば、それぞれの工程において望ましい運転条件を、特別な制限無く決定することができる。 When water is added, conditions for operating the addition apparatus including the above-described addition apparatus can be arbitrarily determined according to each apparatus. Controllable operating conditions include rotational speed, combustion ash charging speed and timing, water charging speed and timing, water addition method, and operating time. A person skilled in the art can determine the desired operating conditions in each step without any particular limitation.
上記の水分の添加方法も、当該技術分野で知られているあらゆる適切な方法を使用することができる。水分の添加方法の例として、例えば定量ポンプ、ローラーポンプ、チューブポンプ、モーノポンプ、自動計量装置付きポンプ、自動流量装置付きポンプなどの方法が挙げられるが、適当な方法はこれらに限られるものではない。 Any appropriate method known in the art can be used for the above-described method of adding moisture. Examples of the method of adding water include, for example, a metering pump, a roller pump, a tube pump, a Mono pump, a pump with an automatic metering device, a pump with an automatic flow device, etc., but an appropriate method is not limited thereto. .
本発明の一態様において、燃焼灰と水を、水分添加装置内に同時に導入することもできる。この場合、燃焼灰が連続的に水分添加装置内に導入されることもできる。同時に、水が連続的に水添加装置内に導入されることもできる。工程の効率および均一化の点から、燃焼灰が自動的に計量されながら水添加装置内に所定の量ずつ導入され、水分の添加量も灰の添加量に応じて、自動的に計算され計量されながら、水分添加装置内に所定の量ずつ導入されることが好ましい。 In one embodiment of the present invention, the combustion ash and water can be simultaneously introduced into the moisture adding device. In this case, the combustion ash can be continuously introduced into the water addition device. At the same time, water can be continuously introduced into the water addition device. From the viewpoint of process efficiency and homogenization, combustion ash is automatically weighed and introduced into the water addition device in a specified amount, and the amount of water added is automatically calculated and metered according to the amount of ash added. However, it is preferable that a predetermined amount is introduced into the moisture adding device.
本発明の一態様においては、燃焼灰に添加する水の量が燃焼灰１００質量部に対して５質量部以上１００質量部以下に調整されることが好ましい。この場合、処理に供される燃焼灰の量に対応して、添加されるべき水の量が決定されるが、水は全量を１回で添加してもよく、複数回に分けて添加してもよく、連続的に添加してもよい。水を複数回に分けて添加する場合、各添加での水添加量は必ずしも均一でなくてもよく、添加ごとに異なる量を添加することもできる。水を連続的に添加する場合、水の添加速度は途中で異なっていてもよく、必ずしも添加開始から添加終了まで一定の流量で添加し続けなければならないわけではない。同様に、水を連続的に添加する場合においても、添加を一時的に中断することもでき、工程の必要に応じて任意のタイミングで添加を再開することもできる。 In 1 aspect of this invention, it is preferable that the quantity of the water added to combustion ash is adjusted to 5 mass parts or more and 100 mass parts or less with respect to 100 mass parts of combustion ash. In this case, the amount of water to be added is determined in accordance with the amount of combustion ash used for the treatment, but the total amount of water may be added at once, or added in multiple portions. It may be added continuously. When water is added in a plurality of times, the amount of water added in each addition is not necessarily uniform, and a different amount can be added for each addition. When water is added continuously, the rate of water addition may be different on the way, and it does not necessarily have to continue to be added at a constant flow rate from the start of addition to the end of addition. Similarly, when water is continuously added, the addition can be temporarily interrupted, and the addition can be resumed at an arbitrary timing according to the necessity of the process.
燃焼灰に添加する水の量が灰１００質量部に対して５質量部未満であると、灰に水を添加する本来の目的の一つである飛散性の防止が十分に達成されないことがある。燃焼灰に添加する水の量が灰１００質量部に対して１００質量部を越えると、燃焼灰自体が多量の水分を含むこととなって燃焼灰の吸水性が失われてしまい、得られた処理物を吸水材などに利用することが困難となることがある。また、水分を多く添加した燃焼灰においては六価クロムの溶出量が多くなる傾向がある。 When the amount of water added to the combustion ash is less than 5 parts by mass with respect to 100 parts by mass of the ash, prevention of scattering, which is one of the original purposes of adding water to the ash, may not be sufficiently achieved. . When the amount of water added to the combustion ash exceeds 100 parts by mass with respect to 100 parts by mass of the ash, the combustion ash itself contains a large amount of water, resulting in loss of water absorption of the combustion ash. It may be difficult to use the processed material as a water absorbing material. In addition, the amount of elution of hexavalent chromium tends to increase in combustion ash to which a large amount of moisture is added.
燃焼灰に水分を添加した後、確認のために燃焼灰の含有水分量を計測することが好ましい。燃焼灰の含有水分計測の方法は、当業者に周知のあらゆる方法を利用することができる。例として、近赤外線水分計、オンライン水分計、光学式水分計、非接触水分計および、赤外線水分計、ハロゲン水分計などの加熱式水分計を利用することができるが、測定手段はこれらに限定されない。 After adding water to the combustion ash, it is preferable to measure the water content of the combustion ash for confirmation. Any method known to those skilled in the art can be used as a method for measuring the moisture content of the combustion ash. For example, a near-infrared moisture meter, an online moisture meter, an optical moisture meter, a non-contact moisture meter, and a heating moisture meter such as an infrared moisture meter and a halogen moisture meter can be used, but the measuring means is limited to these. Not.
燃焼灰に処理剤および水を添加した後に、後処理工程として、本発明の目的および範囲を損なわない限りにおいて、何らかの処理を施してもよい。後処理工程の一例として、養生（灰を袋および箱等に入れて保管すること）、風乾（灰を空気中に曝して保管すること）、乾燥および分級などが含まれるが、これらに限定されるものでもなく、後処理工程を何ら行わないことも可能である。これらの後処理の期間は特に制限されないが、１０時間〜５日間が好ましく、１〜３日間がより好ましい。 After the treatment agent and water are added to the combustion ash, any treatment may be performed as a post-treatment step as long as the object and scope of the present invention are not impaired. Examples of post-processing steps include, but are not limited to, curing (store ash in bags and boxes), air dry (store ash exposed to air), drying and classification. It is also possible that no post-processing steps are performed. The period of these post treatments is not particularly limited, but is preferably 10 hours to 5 days, and more preferably 1 to 3 days.
本発明の一態様である燃焼灰の処理方法は、上述の通り、灰に処理剤および水を添加する工程のみにおいて完結するものである。 As described above, the method for treating combustion ash that is one embodiment of the present invention is completed only in the step of adding the treating agent and water to the ash.
また、本発明の別の態様において、上記の処理剤および水に加えて、さらに、燃焼灰処理物からの有害成分溶出量を減少させる効果のある材料を添加してもよい。上記の材料は、有機酸もしくは有機酸塩、既知の還元剤の全て、あるいは、例えば酸化カルシウム、水酸化カルシウム、亜硫酸カルシウム、炭酸カルシウム、硫酸カルシウムなどのカルシウム系材料が例として挙げられるが、これらに限定されるものではない。上記の材料は、予め水に加えて水溶液または懸濁液とし、これを燃焼灰に添加することもできる。この場合、これらの材料を水分と混合させる方法は当業者に周知のあらゆる方法を使用することができ、一例として撹拌機、混合機、ホモミキサー、スターラー、アジテーターなどが挙げられるが、これらに限定されるものではない。また、これらの材料は予め水に加えずに、燃焼灰に水が添加される前または後に、水とは別に灰に添加されるようにすることもできる。 In another embodiment of the present invention, in addition to the above-mentioned treatment agent and water, a material having an effect of reducing the amount of harmful components eluted from the burned ash product may be added. Examples of the above materials include organic acids or organic acid salts, all known reducing agents, or calcium-based materials such as calcium oxide, calcium hydroxide, calcium sulfite, calcium carbonate, and calcium sulfate. It is not limited to. The above materials can be added in advance to water to form an aqueous solution or suspension, which can be added to the combustion ash. In this case, any method known to those skilled in the art can be used as a method of mixing these materials with moisture, and examples thereof include a stirrer, a mixer, a homomixer, a stirrer, an agitator, and the like. Is not to be done. In addition, these materials may be added to the ash separately from water before or after the water is added to the combustion ash without being added to the water in advance.
本発明によって得られる処理物は、吸水性が良好であり、それ自体有用なものである。本発明の処理物は、その吸水性や保水性を活かして、例えば、吸収材、土壌改良材などの用途に特に好適に使用することができる。本発明によれば、廃棄物である燃焼灰を原料として有用材料を製造することができるため、廃棄物削減、地球環境保全の観点からも好適である。 The treated product obtained by the present invention has good water absorption and is useful per se. The treated product of the present invention can be particularly suitably used for applications such as an absorbent and a soil conditioner, taking advantage of its water absorption and water retention. According to the present invention, a useful material can be produced using combustion ash, which is waste, as a raw material, which is preferable from the viewpoint of waste reduction and global environmental conservation.
以下、本発明を実施するために好適な手順の例を記載するが、本発明は以下の例に何ら限定されるものではない。すなわち、本発明は、以下の実施例に記載する具体的な方法、プロセス、手順、工程、装置、機器、材料、資材、薬品に限定されるものではなく、本発明の目的を損ねない範囲において種々の変更を行うことができる。
なお、特に記載しない場合、本明細書において部や％は重量基準であり、数値範囲はその端点を含むものである。また、実施例、比較例にて得られた処理物は以下の試験方法で、溶出試験を行った。
Hereinafter, although the example of the suitable procedure for implementing this invention is described, this invention is not limited to the following examples at all. That is, the present invention is not limited to the specific methods, processes, procedures, steps, devices, equipment, materials, materials, and chemicals described in the following examples, and in a range that does not impair the object of the present invention. Various changes can be made.
Unless otherwise specified, parts and% in this specification are based on weight, and the numerical range includes the end points. Moreover, the processed material obtained in the Example and the comparative example performed the elution test with the following test methods.
＜試験方法＞
・溶出試験
環境省告示第１８号に準拠し、処理物からの有害物質の溶出を試験した。フッ素はイオンクロマトグラフィーにて、ホウ素・全クロム・六価クロム・鉛はＩＣＰ発光分光分析にて測定した。なお、溶出量基準はフッ素（Ｆ）０．８ｍｇ／Ｌ以下、ホウ素（Ｂ）１ｍｇ／Ｌ以下、六価クロム（Ｃｒ（ＶＩ））０．０５ｍｇ／Ｌ以下、鉛（Ｐｂ）０．０１ｍｇ／Ｌ以下である。
Ａ） フッ素、ホウ素、六価クロム、全クロム、鉛の溶出方法：平成１５年環境省告示第１８号に準じて行なった。すなわち、試料を、粒状品は破砕した後、非金属製である目開き２ｍｍの篩を通過させたもの５０ｇを１０００ｍｌの蓋つきのポリエチレン容器に取り、純水（ｐＨ５．８〜６．３）を５００ｍｌ加えて試料液を調製した。この調製した試料液を、常温、大気圧下で、溶出振とう機を用いて６時間連続振とうした（振とう幅４〜５ｃｍ、振動数２００回／分）。ついで、振とう後の試料液を、３０分間静置した後、毎分約３０００回転で２０分間遠心分離した。上澄み液を孔径０．４５μｍのメンブレンフィルターで濾過し、濾液をとり、定量に必要な量を正確に計り取り、これを検液とした。なお、溶出量基準はフッ素０．８ｍｇ／Ｌ以下、ホウ素１ｍｇ／Ｌ以下、六価クロム０．０５ｍｇ／Ｌ以下、鉛０．０１ｍｇ／Ｌ以下である。
（Ｂ） フッ素溶出量の測定方法：上記検液をイオンクロマトグラフ法により分析し、溶出したフッ素の量を定量した（ＪＩＳ Ｋ ０１０２の３４．２）。
（Ｃ） ホウ素、六価クロム、全クロム、鉛溶出量の測定方法：上記検液をジフェニルカルバジド吸光光度法にて分析し、溶出したホウ素、六価クロム、全クロム、鉛の量を定量した（ＪＩＳ Ｋ ０１０２の６５．２．１）。
（Ｄ） 溶出液のｐＨ：「土懸濁液のｐＨ試験方法」（地盤工学会基準、JGS 0211-2000）に従って、試料に対して５倍量の水を加えて撹拌した試料液のｐＨを測定した。
<Test method>
-Dissolution test In accordance with Ministry of the Environment Notification No. 18, dissolution of harmful substances from treated products was tested. Fluorine was measured by ion chromatography, and boron, total chromium, hexavalent chromium and lead were measured by ICP emission spectroscopic analysis. The elution standard is fluorine (F) 0.8 mg / L or less, boron (B) 1 mg / L or less, hexavalent chromium (Cr (VI)) 0.05 mg / L or less, lead (Pb) 0.01 mg / L. L or less.
A) Fluorine, boron, hexavalent chromium, total chromium, lead elution method: Performed according to 2003 Ministry of the Environment Notification No. 18. That is, after the sample was crushed into granular products, 50 g of a non-metallic sieve having a mesh opening of 2 mm was passed through a 1000 ml polyethylene container with a lid, and pure water (pH 5.8 to 6.3) was added. A sample solution was prepared by adding 500 ml. The prepared sample solution was shaken continuously for 6 hours at room temperature and atmospheric pressure using an elution shaker (shaking width: 4 to 5 cm, vibration frequency: 200 times / min). Next, the sample solution after shaking was allowed to stand for 30 minutes, and then centrifuged at about 3000 rpm for 20 minutes. The supernatant was filtered through a membrane filter having a pore size of 0.45 μm, the filtrate was taken, and the amount required for quantification was accurately measured, and this was used as a test solution. In addition, the elution amount standard is 0.8 mg / L or less of fluorine, 1 mg / L or less of boron, 0.05 mg / L or less of hexavalent chromium, and 0.01 mg / L or less of lead.
(B) Measuring method of fluorine elution amount: The above test solution was analyzed by an ion chromatography method, and the amount of eluted fluorine was quantified (34.2 of JIS K 0102).
(C) Measuring method for elution amount of boron, hexavalent chromium, total chromium and lead: Analyze the above test solution by diphenylcarbazide absorptiometry and quantify the amount of eluted boron, hexavalent chromium, total chromium and lead (JIS K 0102 65.2.1).
(D) pH of eluate: according to “pH test method of soil suspension” (geological engineering society standard, JGS 0211-2000) It was measured.
［実施例１］
＜ペーパースラッジ燃焼灰＞
製紙工場における脱墨フロスおよび流失繊維を主体とする廃棄物（以下「ペーパースラッジ」と呼ぶ）を、燃焼温度約８５０℃、平均滞留時間が１０秒未満の条件でペーパースラッジ用流動床炉にて燃焼させた。この燃焼は、廃棄物の減容化ならびに蒸気および熱エネルギーの回収を目的とするものである。得られた燃焼残渣（ペーパースラッジ燃焼灰）はバグフィルタに捕集された後、貯蔵サイロ内へ移送された。移送された灰を取り出し、以下の処理に供した。
＜新エネルギー燃焼灰＞
石炭７０％、ＲＰＦ１０％、廃タイヤ２０％の比率の原料を、燃焼温度約８５０℃、平均滞留時間が１０秒未満の条件で流動床炉の新エネルギーボイラーで燃焼させた。得られた燃焼残渣（新エネルギー燃焼灰）はバグフィルタに捕集された後、貯蔵サイロ内へ移送された。移送された灰を取り出し、以下の処理に供した。
＜燃焼灰の処理＞
二軸混練機にて上記燃焼灰１００質量部（ペーパースラッジ燃焼灰８０質量部、新エネルギー燃焼灰２０質量部）に対して７１質量部の量の水を添加し、混練して処理物を得た。この際、この水に、燃焼灰１００質量部に対して１質量部の量に相当する量のジエチルジチオカルバミン酸カリウム、５質量部の量に相当する量の二水石膏をあらかじめ加え、ホモミキサーにて溶解残渣が無くなるまで溶解させた。その後、得られた処理物を３日間風乾し、風乾後の処理物について有害物質の溶出試験を行った。
[Example 1]
<Paper sludge combustion ash>
Waste (mainly referred to as “paper sludge”) consisting mainly of deinked floss and run-off fiber in a paper mill is heated in a fluidized bed furnace for paper sludge at a combustion temperature of about 850 ° C. and an average residence time of less than 10 seconds. Burned. This combustion is intended to reduce the volume of waste and recover steam and thermal energy. The obtained combustion residue (paper sludge combustion ash) was collected by a bag filter and then transferred into a storage silo. The transferred ash was taken out and subjected to the following treatment.
<New energy combustion ash>
Raw materials in a ratio of 70% coal, 10% RPF, and 20% waste tire were burned in a new energy boiler of a fluidized bed furnace under conditions of a combustion temperature of about 850 ° C. and an average residence time of less than 10 seconds. The obtained combustion residue (new energy combustion ash) was collected by a bag filter and then transferred into a storage silo. The transferred ash was taken out and subjected to the following treatment.
<Treatment of combustion ash>
In a biaxial kneader, 71 parts by mass of water is added to 100 parts by mass of the combustion ash (80 parts by mass of paper sludge combustion ash, 20 parts by mass of new energy combustion ash) and kneaded to obtain a processed product. It was. At this time, to this water, potassium diethyldithiocarbamate in an amount corresponding to 1 part by mass with respect to 100 parts by mass of combustion ash is added in advance, and dihydrate gypsum in an amount corresponding to 5 parts by mass is added in advance to a homomixer. And dissolved until the dissolution residue disappeared. Thereafter, the obtained treated product was air-dried for 3 days, and a toxic substance elution test was performed on the treated product after air drying.
溶出液のｐＨは１１．２、フッ素の溶出量は０．２４ｍｇ／Ｌ、ホウ素の溶出量は０．２ｍｇ／Ｌ、六価クロムの溶出量は０．０１ｍｇ／Ｌ以下であり、その他の元素の溶出量も土壌汚染対策法の環境基準値以下であった。 PH of eluate is 11.2, elution amount of fluorine is 0.24 mg / L, elution amount of boron is 0.2 mg / L, elution amount of hexavalent chromium is 0.01 mg / L or less, and other elements Was also below the environmental standard value of the Soil Contamination Countermeasures Law.
［実施例２］
実施例１において、燃焼灰をペーパースラッジ燃焼灰７０質量部、新エネルギー燃焼灰３０質量部）とした他は、実施例１と同様にして燃焼灰を処理し、処理物を調製し、有害物質の溶出試験を行った。
溶出液のｐＨは１１．６、フッ素の溶出量は０．１２ｍｇ／Ｌ、ホウ素の溶出量は０．５ｍｇ／Ｌ、六価クロムの溶出量は０．０４８ｍｇ／Ｌであり、その他の元素の溶出量も土壌汚染対策法の環境基準値以下であった。
[Example 2]
In Example 1, except that the combustion ash was changed to 70 parts by weight of paper sludge combustion ash and 30 parts by weight of new energy combustion ash, the combustion ash was treated in the same manner as in Example 1 to prepare a treated product, The dissolution test was conducted.
The pH of the eluate is 11.6, the elution amount of fluorine is 0.12 mg / L, the elution amount of boron is 0.5 mg / L, the elution amount of hexavalent chromium is 0.048 mg / L, and other elements The amount of elution was also below the environmental standard value of the Soil Contamination Countermeasures Law.
［実施例３］
実施例１において、燃焼灰をペーパースラッジ燃焼灰７０質量部、新エネルギー燃焼灰３０質量部とし、ジエチルジチオカルバミン酸カリウムの添加部数を１．５質量部とした他は、実施例１と同様にして燃焼灰を処理し、処理物を調製し、有害物質の溶出試験を行った。
溶出液のｐＨは１１．６、フッ素の溶出量は０．１２ｍｇ／Ｌ、ホウ素の溶出量は０．５ｍｇ／Ｌ、六価クロムの溶出量は０．００９ｍｇ／Ｌであり、その他の元素の溶出量も土壌汚染対策法の環境基準値以下であった。
[Example 3]
In Example 1, the combustion ash was changed to 70 parts by weight of paper sludge combustion ash, 30 parts by weight of new energy combustion ash, and the addition part of potassium diethyldithiocarbamate was 1.5 parts by weight. Combustion ash was treated, a treated product was prepared, and a toxic substance elution test was conducted.
The pH of the eluate was 11.6, the elution amount of fluorine was 0.12 mg / L, the elution amount of boron was 0.5 mg / L, the elution amount of hexavalent chromium was 0.009 mg / L, and other elements The amount of elution was also below the environmental standard value of the Soil Contamination Countermeasures Law.
［実施例４］
実施例１において、燃焼灰をペーパースラッジ燃焼灰７０質量部、新エネルギー燃焼灰３０質量部とし、ジエチルジチオカルバミン酸カリウムの添加部数を２質量部とした他は、実施例１と同様にして燃焼灰を処理し、処理物を調製し、有害物質の溶出試験を行った。
溶出液のｐＨは１１．７、フッ素の溶出量は０．１０ｍｇ／Ｌ、ホウ素の溶出量は０．１ｍｇ／Ｌ、六価クロムの溶出量は０．００２ｍｇ／Ｌであり、その他の元素の溶出量も土壌汚染対策法の環境基準値以下であった。
[Example 4]
In Example 1, the combustion ash was the same as in Example 1 except that the paper ash was 70 parts by weight of paper sludge combustion ash, 30 parts by weight of new energy combustion ash, and 2 parts by weight of potassium diethyldithiocarbamate was added. , Processed products were prepared, and a toxic substance dissolution test was conducted.
The pH of the eluate is 11.7, the elution amount of fluorine is 0.10 mg / L, the elution amount of boron is 0.1 mg / L, the elution amount of hexavalent chromium is 0.002 mg / L, and other elements The amount of elution was also below the environmental standard value of the Soil Contamination Countermeasures Law.
［実施例５］
実施例１において、燃焼灰をペーパースラッジ燃焼灰６０質量部、新エネルギー燃焼灰４０質量部とし、ジエチルジチオカルバミン酸カリウムの添加部数を１．５重量部とした他は、実施例１と同様にして燃焼灰を処理し、処理物を調製し、有害物質の溶出試験を行った。
溶出液のｐＨは１１．６、フッ素の溶出量は０．０８ｍｇ／Ｌ、ホウ素の溶出量は０．３ｍｇ／Ｌ、六価クロムの溶出量は０．０１６ｍｇ／Ｌであり、その他の元素の溶出量も土壌汚染対策法の環境基準値以下であった。
[Example 5]
In Example 1, the combustion ash was changed to 60 parts by weight of paper sludge combustion ash, 40 parts by weight of new energy combustion ash, and the addition part of potassium diethyldithiocarbamate was 1.5 parts by weight. Combustion ash was treated, a treated product was prepared, and a toxic substance elution test was conducted.
The pH of the eluate is 11.6, the fluorine elution amount is 0.08 mg / L, the boron elution amount is 0.3 mg / L, and the hexavalent chromium elution amount is 0.016 mg / L. The amount of elution was also below the environmental standard value of the Soil Contamination Countermeasures Law.
［実施例６］
実施例１において、燃焼灰をペーパースラッジ燃焼灰６０質量部、新エネルギー燃焼灰４０質量部とし、ジエチルジチオカルバミン酸カリウムの添加部数を２重量部とした他は、実施例１と同様にして燃焼灰を処理し、処理物を調製し、有害物質の溶出試験を行った。
溶出液のｐＨは１１．７、フッ素の溶出量は０．０６ｍｇ／Ｌ、ホウ素の溶出量は０．５ｍｇ／Ｌ、六価クロムの溶出量は０．００６ｍｇ／Ｌであり、その他の元素の溶出量も土壌汚染対策法の環境基準値以下であった。
[Example 6]
In Example 1, the combustion ash was the same as in Example 1 except that the paper ash was 60 parts by weight of paper sludge combustion ash, 40 parts by weight of new energy combustion ash, and the addition part of potassium diethyldithiocarbamate was 2 parts by weight. , Processed products were prepared, and a toxic substance dissolution test was conducted.
The pH of the eluate is 11.7, the elution amount of fluorine is 0.06 mg / L, the elution amount of boron is 0.5 mg / L, and the elution amount of hexavalent chromium is 0.006 mg / L. The amount of elution was also below the environmental standard value of the Soil Contamination Countermeasures Law.
［比較例１］
実施例１において、水のみを添加した他は、実施例１と同様にして燃焼灰を処理し、処理物を調製し、有害物質の溶出試験を行った。
溶出液のｐＨは１１．４、フッ素の溶出量は２．７９ｍｇ／Ｌ、ホウ素の溶出量は１．１ｍｇ／Ｌ、六価クロムの溶出量は０．０９０ｍｇ／Ｌであり、土壌汚染対策法の環境基準値を超えていた。
[Comparative Example 1]
In Example 1, except that only water was added, the combustion ash was treated in the same manner as in Example 1, a treated product was prepared, and a toxic substance elution test was performed.
The pH of the eluate is 11.4, the elution amount of fluorine is 2.79 mg / L, the elution amount of boron is 1.1 mg / L, and the elution amount of hexavalent chromium is 0.090 mg / L. The environmental standard value was exceeded.
［比較例２］
実施例１において、ジエチルジチオカルバミン酸カリウムを添加しない他は、実施例１と同様にして燃焼灰を処理し、処理物を調製し、有害物質の溶出試験を行った。
溶出液のｐＨは１１．２、フッ素の溶出量は０．３３ｍｇ／Ｌ、ホウ素の溶出量は０．２ｍｇ／Ｌ、六価クロムの溶出量は０．１１６ｍｇ／Ｌであり、六価クロムの溶出量は土壌汚染対策法の環境基準値を超えていた。
[Comparative Example 2]
In Example 1, except that potassium diethyldithiocarbamate was not added, combustion ash was treated in the same manner as in Example 1 to prepare a treated product, and a toxic substance elution test was performed.
The pH of the eluate is 11.2, the elution amount of fluorine is 0.33 mg / L, the elution amount of boron is 0.2 mg / L, and the elution amount of hexavalent chromium is 0.116 mg / L. The amount of elution exceeded the environmental standard value of the Soil Contamination Countermeasures Law.
［比較例３］
実施例１において、二水石膏を添加しない他は、実施例１と同様にして燃焼灰を処理し、処理物を調製し、有害物質の溶出試験を行った。
溶出液のｐＨは１１．２、フッ素の溶出量は１．０７ｍｇ／Ｌ、ホウ素の溶出量は２．２ｍｇ／Ｌ、六価クロムの溶出量は０．０１４ｍｇ／Ｌであり、フッ素、ホウ素の溶出量は土壌汚染対策法の環境基準値を超えていた。
[Comparative Example 3]
In Example 1, except that dihydrate gypsum was not added, combustion ash was treated in the same manner as in Example 1 to prepare a treated product, and a toxic substance elution test was performed.
The pH of the eluate was 11.2, the elution amount of fluorine was 1.07 mg / L, the elution amount of boron was 2.2 mg / L, and the elution amount of hexavalent chromium was 0.014 mg / L. The amount of elution exceeded the environmental standard value of the Soil Contamination Countermeasures Law.
得られた処理物の評価結果を表１に示す。ジエチルジチオカルバミン酸カリウムと、二水石膏または硫酸第一鉄を添加した実施例１〜６では、フッ素、ホウ素、六価クロム、鉛のいずれに関しても、これら有害成分の溶出量が環境基準値を下回っていた。
灰に処理剤を添加していない比較例１では、フッ素、ホウ素、六価クロムの溶出量が環境基準値を上回っていた。また、二水石膏のみを添加した比較例２においても、六価クロムの溶出量は環境基準値を上回っていた。一方、ジエチルジチオカルバミン酸カリウムのみを添加した比較例３では、フッ素、ホウ素の溶出量が環境基準値を上回っていた。
The evaluation results of the obtained processed product are shown in Table 1. In Examples 1 to 6 to which potassium diethyldithiocarbamate and dihydrate gypsum or ferrous sulfate were added, the leaching amount of these harmful components was lower than the environmental standard value for any of fluorine, boron, hexavalent chromium and lead. It was.
In Comparative Example 1 in which no treating agent was added to the ash, the elution amounts of fluorine, boron, and hexavalent chromium exceeded the environmental standard value. Moreover, also in the comparative example 2 which added only dihydrate gypsum, the elution amount of hexavalent chromium exceeded the environmental standard value. On the other hand, in Comparative Example 3 in which only potassium diethyldithiocarbamate was added, the elution amounts of fluorine and boron exceeded the environmental standard value.
［実施例７］
＜ペーパースラッジ燃焼灰＞
実施例１で使用したペーパースラッジ燃焼灰を使用した。
＜石炭燃焼灰＞
石炭を、燃焼温度約８５０℃、平均滞留時間が１０秒未満の条件で流動床炉の石炭ボイラーで燃焼させた。得られた燃焼残渣（石炭燃焼灰）はバグフィルタに捕集された後、貯蔵サイロ内へ移送された。移送された灰を取り出し、以下の処理に供した。
＜燃焼灰の処理＞
二軸混練機にて上記燃焼灰１００質量部（ペーパースラッジ燃焼灰８０質量部、石炭燃焼灰２０質量部）に対して７１質量部の量の水を添加し、混練して処理物を得た。この際、この水に、燃焼灰１００質量部に対して０．８質量部の量に相当する量のジエチルジチオカルバミン酸カリウム、３質量部の量に相当する量の硫酸第一鉄をあらかじめ加え、ホモミキサーにて溶解残渣が無くなるまで溶解させた。その後、得られた処理物を３日間風乾し、風乾後の処理物について有害物質の溶出試験を行った。
溶出液のｐＨは１１．６、フッ素の溶出量は０．３９ｍｇ／Ｌ、ホウ素の溶出量は０．１ｍｇ／Ｌ以下、六価クロムの溶出量は０．０１ｍｇ／Ｌ以下であり、その他の元素の溶出量も土壌汚染対策法の環境基準値以下であった。
[Example 7]
<Paper sludge combustion ash>
The paper sludge combustion ash used in Example 1 was used.
<Coal combustion ash>
Coal was burned in a fluidized bed furnace coal boiler under conditions of a combustion temperature of about 850 ° C. and an average residence time of less than 10 seconds. The obtained combustion residue (coal combustion ash) was collected by a bag filter and then transferred into a storage silo. The transferred ash was taken out and subjected to the following treatment.
<Treatment of combustion ash>
In a biaxial kneader, 71 parts by mass of water was added to 100 parts by mass of the combustion ash (80 parts by mass of paper sludge combustion ash, 20 parts by mass of coal combustion ash), and kneaded to obtain a processed product. . At this time, to this water, potassium diethyldithiocarbamate in an amount corresponding to an amount of 0.8 parts by mass with respect to 100 parts by mass of combustion ash is added in advance, and an amount of ferrous sulfate corresponding to an amount of 3 parts by mass, It was made to melt | dissolve until the melt | dissolution residue was lost with the homomixer. Thereafter, the obtained treated product was air-dried for 3 days, and a toxic substance elution test was performed on the treated product after air drying.
The pH of the eluate is 11.6, the elution amount of fluorine is 0.39 mg / L, the elution amount of boron is 0.1 mg / L or less, the elution amount of hexavalent chromium is 0.01 mg / L or less, The amount of element elution was also below the environmental standard value of the Soil Contamination Countermeasures Law.
［実施例８］
実施例７において、硫酸第一鉄の添加部数を７質量部とした他は、実施例１と同様にして燃焼灰を処理し、処理物を調製し、有害物質の溶出試験を行った。
溶出液のｐＨは１１．１、フッ素の溶出量は０．１ｍｇ／Ｌ以下、ホウ素の溶出量は０．１ｍｇ／Ｌ以下、六価クロムの溶出量は０．０１ｍｇ／Ｌ以下であり、その他の元素の溶出量も土壌汚染対策法の環境基準値以下であった。
[Example 8]
In Example 7, except that the added part of ferrous sulfate was changed to 7 parts by mass, the combustion ash was treated in the same manner as in Example 1 to prepare a treated product, and a toxic substance elution test was performed.
The pH of the eluate is 11.1, the elution amount of fluorine is 0.1 mg / L or less, the elution amount of boron is 0.1 mg / L or less, the elution amount of hexavalent chromium is 0.01 mg / L or less, and others The amount of element elution was also below the environmental standard value of the Soil Contamination Countermeasures Law.
［実施例９］
実施例７において、ジエチルジチオカルバミン酸カリウムの添加部数を１質量部、硫酸第一鉄の添加部数を７質量部とした他は、実施例１と同様にして燃焼灰を処理し、処理物を調製し、有害物質の溶出試験を行った。
溶出液のｐＨは１１．７、フッ素の溶出量は０．１５ｍｇ／Ｌ、ホウ素の溶出量は０．１ｍｇ／Ｌ以下、六価クロムの溶出量は０．０１ｍｇ／Ｌ以下であり、その他の元素の溶出量も土壌汚染対策法の環境基準値以下であった。
[Example 9]
In Example 7, the combustion ash was treated in the same manner as in Example 1 except that 1 part by weight of potassium diethyldithiocarbamate and 7 parts by weight of ferrous sulfate were added to prepare a treated product. Then, a toxic substance elution test was conducted.
The pH of the eluate is 11.7, the elution amount of fluorine is 0.15 mg / L, the elution amount of boron is 0.1 mg / L or less, the elution amount of hexavalent chromium is 0.01 mg / L or less, The amount of element elution was also below the environmental standard value of the Soil Contamination Countermeasures Law.
［実施例１０］
実施例７において、ジエチルジチオカルバミン酸カリウムの添加部数を１質量部、二水石膏を３質量部添加した他は、実施例８と同様にして燃焼灰を処理し、処理物を調製し、有害物質の溶出試験を行った。
溶出液のｐＨは１１．０、フッ素の溶出量は０．５３ｍｇ／Ｌ、ホウ素の溶出量は０．１ｍｇ／Ｌ以下、六価クロムの溶出量は０．０１ｍｇ／Ｌ以下であり、フッ素の溶出量はやや多いものの土壌汚染対策法の環境基準値以下であった。その他の元素の溶出量も土壌汚染対策法の環境基準値以下であった。
[Example 10]
In Example 7, except that 1 part by weight of potassium diethyldithiocarbamate and 3 parts by weight of dihydrate gypsum were added, the combustion ash was treated in the same manner as in Example 8 to prepare a treated product, The dissolution test was conducted.
The pH of the eluate is 11.0, the elution amount of fluorine is 0.53 mg / L, the elution amount of boron is 0.1 mg / L or less, the elution amount of hexavalent chromium is 0.01 mg / L or less, Although the amount of elution was somewhat large, it was below the environmental standard value of the Soil Contamination Countermeasures Law. The amount of elution of other elements was also below the environmental standard value of the Soil Contamination Countermeasures Law.
［実施例１１］
実施例７において、ジエチルジチオカルバミン酸カリウムの添加部数を１質量部、硫酸第一鉄の添加部数を３質量部、さらに二水石膏を３質量部添加した他は、実施例１と同様にして燃焼灰を処理し、処理物を調製し、有害物質の溶出試験を行った。
溶出液のｐＨは１１．５、フッ素の溶出量は０．１２ｍｇ／Ｌ、ホウ素の溶出量は０．１ｍｇ／Ｌ以下、六価クロムの溶出量は０．０１ｍｇ／Ｌ以下であり、その他の元素の溶出量も土壌汚染対策法の環境基準値以下であった。
[Example 11]
In Example 7, combustion was carried out in the same manner as in Example 1 except that 1 part by weight of potassium diethyldithiocarbamate, 3 parts by weight of ferrous sulfate, and 3 parts by weight of dihydrate gypsum were added. The ash was treated, a treated product was prepared, and a toxic substance elution test was conducted.
The pH of the eluate is 11.5, the elution amount of fluorine is 0.12 mg / L, the elution amount of boron is 0.1 mg / L or less, the elution amount of hexavalent chromium is 0.01 mg / L or less, The amount of element elution was also below the environmental standard value of the Soil Contamination Countermeasures Law.
［実施例１２］
実施例７において、ジエチルジチオカルバミン酸カリウムの添加部数を１質量部、硫酸第一鉄の添加部数を３質量部、さらに二水石膏を７質量部添加した他は、実施例１と同様にして燃焼灰を処理し、処理物を調製し、有害物質の溶出試験を行った。
溶出液のｐＨは１０．９、フッ素の溶出量は０．１ｍｇ／Ｌ以下、ホウ素の溶出量は０．１ｍｇ／Ｌ以下、六価クロムの溶出量は０．０１ｍｇ／Ｌ以下であり、その他の元素の溶出量も土壌汚染対策法の環境基準値以下であった。
[Example 12]
In Example 7, combustion was carried out in the same manner as in Example 1 except that 1 part by weight of potassium diethyldithiocarbamate, 3 parts by weight of ferrous sulfate, and 7 parts by weight of dihydrate gypsum were added. The ash was treated, a treated product was prepared, and a toxic substance elution test was conducted.
PH of eluate is 10.9, elution amount of fluorine is 0.1 mg / L or less, elution amount of boron is 0.1 mg / L or less, elution amount of hexavalent chromium is 0.01 mg / L or less, and others The amount of element elution was also below the environmental standard value of the Soil Contamination Countermeasures Law.
［実施例１３］
実施例７において、ジエチルジチオカルバミン酸カリウムの添加部数を１質量部、硫酸第一鉄の添加部数を７質量部、さらに二水石膏を３質量部添加した他は、実施例１と同様にして燃焼灰を処理し、処理物を調製し、有害物質の溶出試験を行った。
溶出液のｐＨは１０．５、フッ素の溶出量は０．１ｍｇ／Ｌ以下、ホウ素の溶出量は０．１ｍｇ／Ｌ以下、六価クロムの溶出量は０．０１ｍｇ／Ｌ以下であり、その他の元素の溶出量も土壌汚染対策法の環境基準値以下であった。
[Example 13]
In Example 7, combustion was carried out in the same manner as in Example 1 except that 1 part by weight of potassium diethyldithiocarbamate, 7 parts by weight of ferrous sulfate, and 3 parts by weight of dihydrate gypsum were added. The ash was treated, a treated product was prepared, and a toxic substance elution test was conducted.
PH of eluate is 10.5, elution amount of fluorine is 0.1 mg / L or less, elution amount of boron is 0.1 mg / L or less, elution amount of hexavalent chromium is 0.01 mg / L or less, and others The amount of element elution was also below the environmental standard value of the Soil Contamination Countermeasures Law.
［実施例１４］
実施例７において、ジエチルジチオカルバミン酸カリウムの添加部数を１質量部、リン酸を１質量部添加し、硫酸第一鉄及び二水石膏を添加しない他は、実施例１と同様にして燃焼灰を処理し、処理物を調製し、有害物質の溶出試験を行った。
溶出液のｐＨは１１．５、フッ素の溶出量は０．２１ｍｇ／Ｌ、ホウ素の溶出量は０．１６ｍｇ／Ｌ、六価クロムの溶出量は０．０１４ｍｇ／Ｌであり、その他の元素の溶出量も土壌汚染対策法の環境基準値以下であった。
[Example 14]
In Example 7, the addition of 1 part by mass of potassium diethyldithiocarbamate, 1 part by mass of phosphoric acid, and the addition of ferrous sulfate and dihydrate gypsum were the same as in Example 1 except for the combustion ash. After processing, a processed product was prepared, and a dissolution test for harmful substances was performed.
The pH of the eluate is 11.5, the fluorine elution amount is 0.21 mg / L, the boron elution amount is 0.16 mg / L, and the hexavalent chromium elution amount is 0.014 mg / L. The amount of elution was also below the environmental standard value of the Soil Contamination Countermeasures Law.
［実施例１５］
実施例７において、ジエチルジチオカルバミン酸カリウムの添加部数を１質量部、リン酸を３質量部添加し、硫酸第一鉄及び二水石膏を添加しない他は、実施例１と同様にして燃焼灰を処理し、処理物を調製し、有害物質の溶出試験を行った。
溶出液のｐＨは１１．８、フッ素の溶出量は０．１ｍｇ／Ｌ以下、ホウ素の溶出量は０．１４ｍｇ／Ｌ、六価クロムの溶出量は０．０１ｍｇ／Ｌ以下であり、その他の元素の溶出量も土壌汚染対策法の環境基準値以下であった。
[Example 15]
In Example 7, the addition of 1 part by weight of potassium diethyldithiocarbamate, 3 parts by weight of phosphoric acid, and the addition of ferrous sulfate and dihydrate gypsum were the same as in Example 1 except for the combustion ash. After processing, a processed product was prepared, and a dissolution test for harmful substances was performed.
The pH of the eluate is 11.8, the elution amount of fluorine is 0.1 mg / L or less, the elution amount of boron is 0.14 mg / L, the elution amount of hexavalent chromium is 0.01 mg / L or less, The amount of element elution was also below the environmental standard value of the Soil Contamination Countermeasures Law.
［比較例４］
実施例７において、水のみを添加した他は、実施例８と同様にして燃焼灰を処理し、処理物を調製し、有害物質の溶出試験を行った。
溶出液のｐＨは１１．４、フッ素の溶出量は２．４０ｍｇ／Ｌ、ホウ素の溶出量は０．１５ｍｇ／Ｌ、六価クロムの溶出量は０．６８ｍｇ／Ｌであり、フッ素、六価クロムの溶出量は土壌汚染対策法の環境基準値を超えていた。
[Comparative Example 4]
In Example 7, except that only water was added, the combustion ash was treated in the same manner as in Example 8, a treated product was prepared, and a toxic substance elution test was performed.
The pH of the eluate is 11.4, the elution amount of fluorine is 2.40 mg / L, the elution amount of boron is 0.15 mg / L, and the elution amount of hexavalent chromium is 0.68 mg / L. The amount of chromium elution exceeded the environmental standard value of the Soil Contamination Countermeasures Law.
［比較例５］
実施例７において、ジエチルジチオカルバミン酸カリウムの添加部数を１質量部のみを添加した他は、実施例８と同様にして燃焼灰を処理し、処理物を調製し、有害物質の溶出試験を行った。
溶出液のｐＨは１０．７、フッ素の溶出量は１．７１ｍｇ／Ｌ、ホウ素の溶出量は０．２０ｍｇ／Ｌ、六価クロムの溶出量は０．０１ｍｇ／Ｌ以下であり、フッ素の溶出量は土壌汚染対策法の環境基準値を超えていた。
[Comparative Example 5]
In Example 7, except that only 1 part by mass of potassium diethyldithiocarbamate was added, the combustion ash was treated in the same manner as in Example 8, a treated product was prepared, and a toxic substance elution test was performed. .
The pH of the eluate is 10.7, the elution amount of fluorine is 1.71 mg / L, the elution amount of boron is 0.20 mg / L, the elution amount of hexavalent chromium is 0.01 mg / L or less, and elution of fluorine The amount exceeded the environmental standard value of the Soil Contamination Countermeasures Law.
［比較例６］
実施例７において、ジエチルジチオカルバミン酸カリウムを添加せず、二水石膏を５質量部、硫酸第一鉄を７質量部添加した他は、実施例８と同様にして燃焼灰を処理し、処理物を調製し、有害物質の溶出試験を行った。
溶出液のｐＨは９．５、フッ素の溶出量は０．１ｍｇ／Ｌ以下、ホウ素の溶出量は０．１ｍｇ／Ｌ以下、六価クロムの溶出量は０．０５９ｍｇ／Ｌであり、六価クロムの溶出量は土壌汚染対策法の環境基準値を超えていた。
[Comparative Example 6]
In Example 7, the combustion ash was treated in the same manner as in Example 8, except that potassium diethyldithiocarbamate was not added, 5 parts by weight of dihydrate gypsum and 7 parts by weight of ferrous sulfate were added. And a toxic substance elution test was conducted.
The pH of the eluate is 9.5, the elution amount of fluorine is 0.1 mg / L or less, the elution amount of boron is 0.1 mg / L or less, and the elution amount of hexavalent chromium is 0.059 mg / L. The amount of chromium elution exceeded the environmental standard value of the Soil Contamination Countermeasures Law.
得られた処理物の評価結果を表２に示す。ジエチルジチオカルバミン酸カリウムと、二水石膏、硫酸第一鉄またはリン酸を添加した実施例７〜１５では、フッ素、ホウ素、六価クロム、鉛のいずれに関しても、これら有害成分の溶出量が環境基準値を下回っていた。
灰に処理剤を添加していない比較例４では、フッ素、六価クロムの溶出量が環境基準値を上回っていた。また、ジエチルジチオカルバミン酸カリウムのみを添加した比較例５では、フッ素の溶出量が環境基準値を上回っていた。一方、二水石膏と硫酸第一鉄を添加した比較例６においては、六価クロムの溶出量は環境基準値を上回っていた。
Table 2 shows the evaluation results of the obtained processed products. In Examples 7 to 15 to which potassium diethyldithiocarbamate and dihydrate gypsum, ferrous sulfate, or phosphoric acid were added, the amount of elution of these harmful components was the environmental standard for any of fluorine, boron, hexavalent chromium, and lead. It was below the value.
In Comparative Example 4 in which no treating agent was added to the ash, the elution amount of fluorine and hexavalent chromium exceeded the environmental standard value. In Comparative Example 5 in which only potassium diethyldithiocarbamate was added, the elution amount of fluorine exceeded the environmental standard value. On the other hand, in Comparative Example 6 in which dihydrate gypsum and ferrous sulfate were added, the elution amount of hexavalent chromium exceeded the environmental standard value.
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