JP7117199B2 - Combustion ash disposal method and reuse method - Google Patents
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- 238000002485 combustion reaction Methods 0.000 title claims description 107
- 238000000034 method Methods 0.000 title claims description 44
- 230000005291 magnetic effect Effects 0.000 claims description 51
- 239000000446 fuel Substances 0.000 claims description 49
- 150000003377 silicon compounds Chemical class 0.000 claims description 40
- 238000007885 magnetic separation Methods 0.000 claims description 38
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000010703 silicon Substances 0.000 claims description 28
- 229910052710 silicon Inorganic materials 0.000 claims description 28
- 239000003208 petroleum Substances 0.000 claims description 11
- 229910001172 neodymium magnet Inorganic materials 0.000 claims description 9
- 239000002956 ash Substances 0.000 description 65
- 239000000126 substance Substances 0.000 description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 239000006148 magnetic separator Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 8
- 239000010881 fly ash Substances 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 239000003245 coal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000002006 petroleum coke Substances 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 150000002506 iron compounds Chemical class 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 150000002816 nickel compounds Chemical class 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
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- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000001931 thermography Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012717 electrostatic precipitator Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Description
本発明は、燃焼灰の処理方法および再使用方法に関し、詳しくは、石油系及び石炭系燃料等を燃焼させた後、生成された燃焼灰からケイ素化合物を磁選により除去することにより、燃焼灰を再度燃料として使用可能とする方法に関する。 The present invention relates to a method for treating and reusing combustion ash, and more specifically, after burning petroleum-based and coal-based fuels, etc., the combustion ash is removed by magnetic separation to remove silicon compounds from the generated combustion ash. The present invention relates to a method for making it usable as fuel again.
石油コークスや重油などの石油系燃料及び石炭系燃料の燃焼によって発生する燃焼灰は、これらの燃料の燃焼条件にもよるが、通常、未燃焼カーボン；石油系燃料に含まれるケイ素化合物、ニッケル化合物、鉄化合物などの金属化合物を主体とする灰分；および燃焼排ガスを脱硝するために還元剤として注入されるアンモニアガスと当該排ガス中に含まれる硫黄酸化物との反応により生成する、水に可溶性の硫安（硫酸アンモニウム）の３成分の混合物である。このうち未燃焼カーボンを燃料用などに有効活用する場合にはケイ素化合物が障害になる。それはケイ素化合物がボイラーに対して熱伝導率の低下を引き起こすからである。この観点より燃焼灰や廃棄物からケイ素化合物を除去する技術が必要となり、ケイ素化合物除去技術が、下記に示すように従来からいくつか提案されている。 Combustion ash generated by the combustion of petroleum-based fuels such as petroleum coke and heavy oil and coal-based fuels, depending on the combustion conditions of these fuels, is usually unburned carbon; silicon compounds contained in petroleum-based fuels, nickel compounds , ash mainly composed of metal compounds such as iron compounds; It is a ternary mixture of ammonium sulfate (ammonium sulfate). Of these, silicon compounds pose an obstacle to the effective use of unburned carbon as fuel. This is because silicon compounds cause a reduction in thermal conductivity for boilers. From this point of view, a technique for removing silicon compounds from combustion ash and waste is required, and several techniques for removing silicon compounds have been conventionally proposed as shown below.
特許文献１および２には、ＮａＯＨ溶液で燃焼灰中のケイ素化合物を浸出させてケイ素化合物を分離する方法が開示されている。
特許文献３には、硫黄を含む添加物を添加した廃棄物から、分離選別装置で金属化合物を分離する方法が開示されている。
Patent Documents 1 and 2 disclose a method of leaching silicon compounds in combustion ash with a NaOH solution to separate the silicon compounds.
Patent Literature 3 discloses a method for separating metal compounds from waste to which additives containing sulfur have been added, using a separation and sorting device.
また、特許文献４には、重油燃焼飛灰を磁選して、バナジウム、鉄、ニッケルを分離回収する方法が開示されている。さらに特許文献５には、二酸化ケイ素を含む循環流動床フライアッシュを磁選し、鉄を除去する方法が開示されている。 Further, Patent Document 4 discloses a method of magnetically separating heavy oil combustion fly ash to separate and recover vanadium, iron, and nickel. Furthermore, Patent Document 5 discloses a method of magnetically separating fly ash in a circulating fluidized bed containing silicon dioxide to remove iron.
しかし、上記特許文献１～３に開示されたＮａＯＨや硫黄添加物を用いる方法は、コストが大きいだけでなく、未燃焼カーボンを燃料用に有効活用する際にはナトリウム化合物や硫黄化合物がボイラー腐食の原因となるので、ＮａＯＨや硫黄添加物を除去する工程が必要になるという短所がある。 However, the methods using NaOH and sulfur additives disclosed in Patent Documents 1 to 3 are not only costly, but also sodium compounds and sulfur compounds cause boiler corrosion when unburned carbon is effectively used for fuel. , so there is a disadvantage that a process for removing NaOH and sulfur additives is required.
また燃焼灰の磁選は、通常、上記特許文献４、５に開示された方法のように、バナジウム、鉄、ニッケルのいずれかの金属に注目して行うものであり、ケイ素化合物等のその他の元素を含む成分は、磁選能力の差異により磁選により磁着されない非磁性体側に回収されると考えられている。 In addition, magnetic separation of combustion ash is usually performed by focusing on any metal of vanadium, iron, and nickel, as in the methods disclosed in Patent Documents 4 and 5, and other elements such as silicon compounds. It is believed that components containing are collected on the non-magnetic side, which is not magnetized by magnetic separation due to the difference in magnetic separation ability.
本発明はこのような事情に鑑み、石油系及び石炭系燃料等の燃料を燃焼させて生成される燃焼灰から、簡易に、実用的かつ有効にケイ素化合物を除去することにより燃料を有効に再使用できる方法を提供することを目的とする。 In view of such circumstances, the present invention effectively recycles fuel by simply, practically and effectively removing silicon compounds from combustion ash produced by burning fuel such as petroleum and coal fuel. The purpose is to provide a method that can be used.
本発明者らは上記課題を解決すべく、鋭意検討した結果、石油系燃料等の燃焼灰を１．０Ｔ以上の磁力にて磁選した場合、燃焼灰よりケイ素化合物を良い効率で除去でき、燃焼灰を燃料として再使用できることを見出した。 In order to solve the above problems, the present inventors have made intensive studies, and as a result, when combustion ash such as petroleum fuel is magnetically separated with a magnetic force of 1.0 T or more, silicon compounds can be removed from combustion ash with good efficiency. We have found that the ash can be reused as fuel.
本発明の要旨は以下の通りである。
［１］ 燃焼工程にて燃料を燃焼して発生した燃焼灰に対し、１．０テスラ以上の磁力で磁選を行い、前記燃焼灰からケイ素化合物を除去する磁選工程を有する燃焼灰の処理方法。
［２］ 前記磁選工程において、磁選に用いる磁石がネオジム磁石または電磁石である、前記［１］に記載の燃焼灰の処理方法。
［３］ 前記燃焼工程において、燃料を燃焼する燃焼温度が１３００℃以上２０００℃以下である、前記［１］または［２］に記載の燃焼灰の処理方法。
［４］ 前記燃焼工程において、ボイラー燃焼炉、電気炉、ロータリーキルン、溶鉱炉または高炉で燃料を燃焼する、前記［１］～［３］のいずれかに記載の燃焼灰の処理方法。［５］ 燃焼灰に対し１．０テスラ以上の磁力で磁選を行い、前記燃焼灰からケイ素化合物を除去する磁選工程を経て得られたケイ素化合物除去済みの燃焼灰を燃焼することを特徴とする燃焼灰の再使用方法。
The gist of the present invention is as follows.
[1] A method for treating combustion ash, comprising a magnetic separation step of magnetically separating combustion ash generated by burning fuel in a combustion step with a magnetic force of 1.0 Tesla or more to remove silicon compounds from the combustion ash.
[2] The method for treating combustion ash according to [1] above, wherein in the magnetic separation step, the magnet used for the magnetic separation is a neodymium magnet or an electromagnet.
[3] The method for treating combustion ash according to [1] or [2], wherein in the combustion step, the combustion temperature for burning the fuel is 1300°C or higher and 2000°C or lower.
[4] The method for treating combustion ash according to any one of [1] to [3], wherein in the combustion step, the fuel is burned in a boiler combustion furnace, an electric furnace, a rotary kiln, a blast furnace or a blast furnace. [5] Combustion ash is subjected to magnetic separation with a magnetic force of 1.0 Tesla or more, and the silicon compound-removed combustion ash obtained through the magnetic separation step of removing silicon compounds from the combustion ash is burned. How to reuse combustion ash.
本発明によれば、石油系燃料または石炭系燃料等を燃焼させ、生成された燃焼灰を磁選することで、添加物を用いずとも、燃焼灰から効率よくケイ素化合物を除去することにより、燃料を有効に再使用する方法を提供することができる。またその燃焼灰からケイ素化合物だけでなく、鉄化合物、ニッケル化合物等の灰分も除去されているので、本発明のケイ素化合物の除去方法を施した後の燃焼灰は再び燃料として有効に活用できる。 According to the present invention, by burning petroleum-based fuel or coal-based fuel and magnetically separating the generated combustion ash, silicon compounds can be efficiently removed from the combustion ash without using additives. can provide a way to effectively reuse the In addition, since not only silicon compounds but also ash such as iron compounds and nickel compounds are removed from the combustion ash, the combustion ash after applying the silicon compound removal method of the present invention can be effectively used again as fuel.
以下、本発明の実施するための形態について説明する。
本発明に係る燃焼灰の処理方法は、燃焼灰から１．０テスラ以上の磁力で磁選を行い、ケイ素化合物を除去する磁選工程を含む。また、燃料を燃焼させて燃焼灰を生成する燃焼工程や、前記磁選工程を経た灰を燃焼する前記燃焼灰の再使用工程を含んでいてもよい。前記再使用工程を含む燃焼灰の処理方法は、燃焼灰の再使用方法として把握することができる。
BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments for carrying out the present invention will be described.
A method for treating combustion ash according to the present invention includes a magnetic separation step of magnetically separating combustion ash with a magnetic force of 1.0 Tesla or more to remove silicon compounds. The method may also include a combustion step of burning fuel to generate combustion ash, and a combustion ash reuse step of burning ash that has undergone the magnetic separation step. The combustion ash disposal method including the reuse step can be grasped as a combustion ash reuse method.
［燃焼工程］
本工程で使用できる燃料としては、石油コークス、重油などの石油系燃料、および石炭などの石炭系燃料等を挙げることができる。前記燃料は、火力発電所などにおいて燃焼され、発電など種々の目的のために使用される。燃料の燃焼に用いられる装置としては、たとえばボイラー燃焼炉、電気炉、ロータリーキルン、溶鉱炉、高炉等が挙げられる。
[Combustion process]
Examples of the fuel that can be used in this step include petroleum-based fuels such as petroleum coke and heavy oil, and coal-based fuels such as coal. The fuel is combusted in a thermal power plant or the like and used for various purposes such as power generation. Apparatuses used for burning fuel include, for example, boiler combustion furnaces, electric furnaces, rotary kilns, blast furnaces, and blast furnaces.
燃焼灰とは、前記燃料を燃焼させた後に残る煤塵である。前記燃焼灰には、燃焼飛灰およびクリンカも含まれる。燃焼飛灰とは、前記燃料を燃焼させた時に発生する排ガスから、電気集塵機やバグフィルターを使用して回収された煤塵である。クリンカとは、前記燃料を燃焼させた後に、ボイラー燃焼炉の底部から排出される燃え残り物である。さらに、燃焼灰を更に焼成し、金属酸化物や硫黄分になった焼成燃焼灰なども本発明で使用される燃焼灰に含まれる。 Combustion ash is the dust that remains after burning the fuel. The combustion ash also includes combustion fly ash and clinker. Combustion fly ash is dust collected from the exhaust gas generated when the fuel is burned using an electrostatic precipitator or a bag filter. Clinker is the residue discharged from the bottom of a boiler combustion furnace after burning said fuel. Furthermore, combustion ash used in the present invention also includes calcined combustion ash that has been further calcined and converted into metal oxides and sulfur content.
本発明は、前記燃焼灰を燃料として使用することを可能にすることにより、燃料の再使用を実現する方法である。
燃焼灰には、前述のとおり、未燃焼カーボン、ケイ素化合物、ニッケル化合物、鉄化合物などの金属化合物、および硫安（硫酸アンモニウム）などが含まれる。ケイ素化合物は、ボイラー等に対する熱伝導率の低下などの弊害をもたらすので、燃焼灰を燃料として再使用する場合には、燃焼灰からケイ素化合物を除去することが必要である。
The present invention is a method for realizing fuel reuse by enabling the combustion ash to be used as fuel.
As described above, the combustion ash includes unburned carbon, silicon compounds, nickel compounds, metal compounds such as iron compounds, ammonium sulfate, and the like. Since silicon compounds cause adverse effects such as lowering the thermal conductivity of boilers and the like, it is necessary to remove the silicon compounds from the combustion ash when reusing the combustion ash as fuel.
燃焼灰に含まれるケイ素化合物としては、二酸化ケイ素、アルミノケイ酸塩およびケイ酸カリウム、ケイ酸ナトリウム等のケイ酸塩等を挙げることができる。
燃焼灰中に含まれるケイ素化合物の量は、使用される燃料の種類や燃焼方法などによって変動はあるものの、通常、ケイ素元素換算で０．１～２．５質量％の範囲である。
Silicon compounds contained in the combustion ash include silicon dioxide, aluminosilicates and silicates such as potassium silicate and sodium silicate.
The amount of silicon compound contained in the combustion ash varies depending on the type of fuel used, the combustion method, etc., but is usually in the range of 0.1 to 2.5% by mass in terms of silicon element.
燃焼灰は、前記燃料を燃焼させることにより生成される。燃焼工程の燃焼温度は、好ましくは５００℃以上であり、より好ましくは６００℃以上であり、更に好ましくは８００℃以上、更により好ましくは１３００℃以上である。燃焼温度は、好ましくは２０００℃以下である。燃焼温度が５００℃以上であれば、理由は明らかではないが燃焼灰中の金属分の凝集が十分に行われ、ケイ素化合物が磁性金属に付着すると推測され、その結果、後の磁選工程で、ケイ素化合物が磁性金属とともに磁着され、ケイ素化合物の磁選効率が上昇すると考えられる。 Combustion ash is produced by burning the fuel. The combustion temperature in the combustion step is preferably 500° C. or higher, more preferably 600° C. or higher, still more preferably 800° C. or higher, still more preferably 1300° C. or higher. The combustion temperature is preferably below 2000°C. If the combustion temperature is 500 ° C. or higher, the metal content in the combustion ash is sufficiently agglomerated, although the reason is not clear, and it is speculated that the silicon compound adheres to the magnetic metal. It is thought that the silicon compound is magnetized together with the magnetic metal, and the magnetic separation efficiency of the silicon compound increases.
前記燃焼温度は、ボイラー燃焼炉にて前記燃料を燃焼する場合には、サーモグラフィカメラ（フリアーシステムズジャパン株式会社.製、ＦＬＩＲ（登録商標） Ｅ９５）を用いて、ボイラー内の過熱器からの放射光を受け測定したときに得られた温度であり、電気炉にて前記燃料を燃焼する場合には、炉内温度をＪＩＳ Ｃ１６０２－２０１５に規定されたＲ型熱電対にて測定したときに得られた温度である。
燃焼工程は、酸化雰囲気であれば特に限定されない。
When the fuel is burned in a boiler combustion furnace, the combustion temperature is measured using a thermography camera (FLIR (registered trademark) E95, manufactured by FLIR Systems Japan Co., Ltd.), and the radiation from the superheater in the boiler. It is the temperature obtained when the light is received and measured, and when the fuel is burned in an electric furnace, the temperature inside the furnace is measured with an R-type thermocouple specified in JIS C1602-2015. is the temperature
The combustion process is not particularly limited as long as it is an oxidizing atmosphere.
［磁選工程］
磁選工程においては、前記燃焼灰からケイ素化合物を磁選により除去する。前述のとおり、前記燃焼工程において得られた燃焼灰においては、ケイ素化合物が磁性金属に付着されていて、燃焼灰に磁選を行うことにより、ケイ素化合物が磁性金属とともに磁着され、ケイ素化合物が効率的に除去される。
[Magnetic separation process]
In the magnetic separation step, silicon compounds are removed from the combustion ash by magnetic separation. As described above, in the combustion ash obtained in the combustion step, the silicon compound is attached to the magnetic metal, and by performing magnetic separation on the combustion ash, the silicon compound is magnetically attached together with the magnetic metal, and the silicon compound is efficiently effectively removed.
磁選の方法は、前記燃焼灰からケイ素化合物除去することができれば、特に制限されない。磁選は、乾式による磁選であっても、湿式による磁選であってもよい。磁選は、磁選機を用いて磁着物を選別する方法であってもよく、磁選機を用いず、磁石に燃焼灰を接触させ、磁着物を選別する方法であってもよい。磁選機としては、高勾配磁選機、ドラム型磁選機、吊り下げ磁選機等を挙げることができる。 The magnetic separation method is not particularly limited as long as the silicon compound can be removed from the combustion ash. The magnetic separation may be dry magnetic separation or wet magnetic separation. Magnetic separation may be a method of sorting magnetic substances using a magnetic separator, or a method of bringing combustion ash into contact with a magnet to sort magnetic substances without using a magnetic separator. Examples of the magnetic separator include a high-gradient magnetic separator, a drum-type magnetic separator, and a suspended magnetic separator.
磁選に用いる磁石は、特に制限はないが、ネオジム磁石、電磁石等が好ましい。これらの磁石を用いると、燃焼灰中のケイ素化合物を効率的に磁着することができる。
磁選工程における磁選の磁力としては、１．０テスラ以上であり、好ましくは１．２テスラ以上、より好ましくは１．５テスラ以上である。１．０テスラ以上の場合、燃焼灰中の微粒金属を良好な磁選効率にて分離でき、ケイ素化合物の磁選を効率よく分離することができる。磁力の上限は、好ましくは４．０テスラである。
Magnets used for magnetic separation are not particularly limited, but neodymium magnets, electromagnets, and the like are preferable. By using these magnets, silicon compounds in combustion ash can be efficiently magnetized.
The magnetic force for magnetic separation in the magnetic separation step is 1.0 tesla or more, preferably 1.2 tesla or more, and more preferably 1.5 tesla or more. In the case of 1.0 tesla or more, fine metal particles in the combustion ash can be separated with good magnetic separation efficiency, and silicon compounds can be efficiently separated by magnetic separation. The upper limit of magnetic force is preferably 4.0 Tesla.
［再使用工程］
再使用工程においては、前記磁選工程にて燃焼灰からケイ素化合物を除去した灰を、燃焼炉へ投入し燃料として再使用する。
磁選工程にてケイ素化合物を除去した灰は、２５ｍＪ／ｋｇ以上の熱量を持ち、炉ボイラーに対して熱伝導率の低下を引き起こす灰中のケイ素化合物濃度も０．６質量％以下と低いことから、燃料として活用することができる。
[Reuse process]
In the reuse step, the ash obtained by removing silicon compounds from the combustion ash in the magnetic separation step is put into a combustion furnace and reused as fuel.
The ash from which silicon compounds have been removed in the magnetic separation process has a calorific value of 25 mJ/kg or more, and the silicon compound concentration in the ash, which causes a decrease in thermal conductivity to the furnace boiler, is as low as 0.6% by mass or less. , can be used as fuel.
磁選工程にてケイ素化合物を除去した灰の燃焼箇所は限定されないが、ボイラー燃焼炉や電気炉、ロータリーキルン、溶鉱炉、高炉などに投入し、燃料として使用することができる。粉体燃料のボイラー燃焼炉の場合には粉体燃料に混合し、液体燃料のボイラー燃焼炉の場合には液体燃料用とは別に設けた粉体投入口より投入することができる。 The ash from which the silicon compound has been removed in the magnetic separation process is not limited in its burning location, but it can be put into a boiler combustion furnace, an electric furnace, a rotary kiln, a blast furnace, a blast furnace, etc., and used as fuel. In the case of a boiler combustion furnace for powder fuel, the powder can be mixed with the powder fuel.
磁選工程を経てケイ素化合物を除去した燃焼灰の、新品の燃料に対する比率は限定されないが、好ましくは５０質量％以下、より好ましくは３０質量％以下、特に好ましくは１０質量％以下である。 The ratio of the combustion ash from which the silicon compound has been removed through the magnetic separation process to the new fuel is not limited, but is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 10% by mass or less.
以下、実施例および比較例を示して本発明を詳細に説明するが、以下の具体例に限定されるものではない。
実施例中の「非磁着物」は、燃焼灰が磁場領域に接触したときに磁石に付着しなかった成分、「磁着物」は、燃焼灰が磁場領域に接触したときに磁石に付着した成分である。
The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to the following specific examples.
"Non-magnetic substances" in the examples are the components that did not adhere to the magnet when the combustion ash came into contact with the magnetic field region, and "magnetic substances" are the components that adhered to the magnet when the combustion ash came into contact with the magnetic field region. is.
実施例で評価されるケイ素元素の残存率および除去率の算出は以下の式に従って行った。
ケイ素元素の残存率（％）＝［非磁着物中のケイ素元素質量／（非磁着物中のケイ素元素質量＋磁着物中のケイ素元素質量）］×１００
ケイ素元素の除去率（％）＝［磁着物中のケイ素元素質量／（非磁着物中のケイ素元素質量＋磁着物中のケイ素元素質量）］×１００
ケイ素元素の定量は以下の方法で行った。
The residual ratio and removal ratio of silicon element evaluated in the examples were calculated according to the following equations.
Residual ratio of silicon element (%) = [mass of silicon element in non-magnetic substance/(mass of silicon element in non-magnetic substance + mass of silicon element in magnetic substance)] × 100
Removal rate of silicon element (%) = [mass of silicon element in magnetic deposit / (mass of silicon element in non-magnetic deposit + mass of silicon element in magnetic deposit)] × 100
The amount of silicon element was quantified by the following method.
サンプル０．１ｇに、リン酸５ｍＬ（純正化学株式会社製、特級）、塩酸４ｍＬ（純正化学株式会社製、特級）、フッ酸２．５ｍＬ（純生化学株式会社製、特級４６％～４８％）および硝酸２ｍＬ（関東化学株式会社製、電子工業用硝酸１．４２ＥＬ）を加え、マイクロウェーブ分解／反応装置（株式会社アクタック製、ＭＷＳ３＋）に入れ、酸分解を行った。 To 0.1 g of sample, 5 mL of phosphoric acid (manufactured by Junsei Chemical Co., Ltd., special grade), 4 mL of hydrochloric acid (manufactured by Junsei Chemical Co., Ltd., special grade), 2.5 mL of hydrofluoric acid (manufactured by Junsei Kagaku Co., Ltd., special grade 46% to 48%) and 2 mL of nitric acid (manufactured by Kanto Kagaku Co., Ltd., nitric acid for electronic industry 1.42EL) was added, and the mixture was placed in a microwave decomposition/reactor (MWS3+, manufactured by Actac Co., Ltd.) for acid decomposition.
マイクロウェーブ加熱分解は以下の条件（１）～（５）で行った。
（１）５分間で１９０℃まで上昇させ、５分間１９０℃に維持した。
（２）２分間で２１０℃まで上昇させ、５分間２１０℃に維持した。
（３）２分間で２３０℃まで上昇させ、２５分間２３０℃に維持した。
（４）１分間で１００℃まで下げ操作を終了した。
（５）上記一連の分解操作を２回繰り返した。
Microwave thermal decomposition was performed under the following conditions (1) to (5).
(1) The temperature was increased to 190°C in 5 minutes and maintained at 190°C for 5 minutes.
(2) raised to 210°C in 2 minutes and maintained at 210°C for 5 minutes;
(3) raised to 230°C in 2 minutes and maintained at 230°C for 25 minutes;
(4) The temperature was lowered to 100°C in 1 minute, and the operation was completed.
(5) The above series of decomposition operations were repeated twice.
得られた酸分解液を２５０ｍＬのメスフラスコに全量移し、２５０ｍＬまで超純水（メルク株式会社製、Ｓｙｎｅｒｇｙ ＵＶ）にてメスアップしたものを分析サンプルとした。ＪＩＳ Ｋ０１１６－２０１４に則り、ＩＣＰ－ＡＥＳ（株式会社島津製作所製、ＩＣＰＳ－８１００）により分析サンプルを測定し、ケイ素元素を定量した。 The whole amount of the obtained acid decomposition solution was transferred to a 250 mL volumetric flask, and the volume was increased to 250 mL with ultrapure water (manufactured by Merck Ltd., Synergy UV) to obtain an analysis sample. According to JIS K0116-2014, the analysis sample was measured by ICP-AES (manufactured by Shimadzu Corporation, ICPS-8100) to quantify the silicon element.
（実施例１）
石油系燃料である石油コークス２０．０ｇを蒸発皿に載せ電気炉（ヤマト科学株式会社製、ＦＰ４１０）に入れ、酸化雰囲気にて燃焼温度５００℃で６．５時間燃焼し、燃焼灰を得た。得られた燃焼灰を室温まで冷却した後、ディスポトレー（アズワン株式会社製、ＤＴ－２）に１．４テスラのネオジム磁石（株式会社サンギョウサプライ製、マグネットバー、直径２５ｍｍ、長さ１５０ｍｍ、１２，０００Ｇ（１４，０００Ｇ）、耐熱温度１２０℃）を置き、燃焼灰をネオジム磁石にふりかけ、非磁着物を振り落とした。振り落とされた非磁着物をネオジム磁石にふりかけ、振り落とす手順を、新たな磁着物が生じなくなるまで繰り返し、非磁着物と磁着物に分離した。非磁着物と磁着物をそれぞれ電気炉（ヤマト科学株式会社製、ＦＰ４１０）に入れ、１１０℃にて２時間乾燥した。得られた非磁着物および磁着物の質量を測定し、上記方法によりケイ素元素を定量し、上記式に従い、ケイ素元素の残存率および除去率を求めた。結果を表１に示す。
(Example 1)
20.0 g of petroleum coke, which is a petroleum-based fuel, was placed on an evaporating dish, placed in an electric furnace (FP410, manufactured by Yamato Scientific Co., Ltd.), and burned at a combustion temperature of 500 ° C. for 6.5 hours in an oxidizing atmosphere to obtain combustion ash. . After cooling the obtained combustion ash to room temperature, a 1.4 Tesla neodymium magnet (manufactured by Sangyo Supply Co., Ltd., magnet bar, diameter 25 mm, length 150 mm, 12 ,000 G (14,000 G), heat resistant temperature 120° C.), the combustion ash was sprinkled on the neodymium magnet, and the non-magnetic substance was shaken off. The procedure of sprinkling the shaken-off non-magnetic substance onto the neodymium magnet and shaking it off was repeated until no new magnetic substance was generated, thereby separating the non-magnetic substance and the magnetic substance. The non-magnetic substance and the magnetic substance were placed in an electric furnace (FP410 manufactured by Yamato Scientific Co., Ltd.) and dried at 110° C. for 2 hours. The masses of the obtained non-magnetic and magnetic substances were measured, the silicon element was quantified by the above method, and the residual ratio and removal ratio of the silicon element were determined according to the above formula. Table 1 shows the results.
（実施例２）
石油コークス２０．０ｇを燃焼温度１，０００℃で３時間燃焼して燃焼灰を得た点以外は、実施例１と同様に行い、ケイ素元素の残存率および除去率を求めた。結果を表１に示す。
(Example 2)
Except that 20.0 g of petroleum coke was burned at a combustion temperature of 1,000° C. for 3 hours to obtain combustion ash, the same procedure as in Example 1 was performed to determine the residual ratio and removal ratio of silicon element. Table 1 shows the results.
（実施例３）
石油系燃料をボイラーにて燃焼温度１４００℃で６秒間燃焼させて、発生した排ガスから電気集塵機で燃焼飛灰を捕集した。前記燃焼温度は、サーモグラフィカメラ（フリアーシステムズジャパン株式会社製、ＦＬＩＲ（登録商標） Ｅ９５）を用いて、ボイラー内の過熱器からの放射光を受けて測定したときに得られた温度とした。この燃焼飛灰２０．０ｇを１００ｍＬのポリプロピレン製ボトル（株式会社サンプラテック製、アイボーイ）に入れ、純水６０．０ｇを加え、２５質量％スラリー溶液とした。スラリー溶液を攪拌後、溶液に１．４テスラのネオジム磁石（株式会社サンギョウサプライ製、マグネットバー、直径２５ｍｍ、長さ１５０ｍｍ、１２，０００Ｇ（１４，０００Ｇ）、耐熱温度１２０℃）を入れ、約５秒後液面より上に持ち上げた。磁着物が磁着したネオジム磁石をチャック付きポリ袋（株式会社生産日本社製、ユニパックＨ－８、ポリエチレン製）内に挿入し、ポリ袋でネオジム磁石に磁着した磁着物をポリ袋内にこそぎ落とし、磁着物をスラリーから分離した。上記一連の磁選操作を、新たな磁着物が生じなくなるまで繰り返し、非磁着物と磁着物を分離した。得られた非磁着物および磁着物の質量を測定し、上記方法によりケイ素元素を定量し、上記式に従い、ケイ素元素の残存率および除去率を求めた。結果を表１に示す。
(Example 3)
A petroleum -based fuel was burned at a combustion temperature of 1400 ° C. for 6 seconds in a boiler, and combustion fly ash was collected from the generated exhaust gas with an electric dust collector. The combustion temperature was measured using a thermography camera (FLIR (registered trademark) E95, manufactured by FLIR Systems Japan KK) while receiving radiant light from a superheater in a boiler. 20.0 g of this combustion fly ash was placed in a 100 mL polypropylene bottle (manufactured by Sun Platec Co., Ltd., IBOY), and 60.0 g of pure water was added to obtain a 25% by mass slurry solution. After stirring the slurry solution, a 1.4 Tesla neodymium magnet (manufactured by Sangyo Supply Co., Ltd., magnet bar, diameter 25 mm, length 150 mm, 12,000 G (14,000 G), heat resistance temperature 120 ° C.) was added to the solution, and After 5 seconds, it was lifted above the liquid surface. A neodymium magnet magnetically attached to a magnetic substance is inserted into a plastic bag with a zipper (manufactured by Sansan Nihon Co., Ltd., Unipack H-8, made of polyethylene), and the magnetic substance magnetically attracted to the neodymium magnet is inserted into the plastic bag. Scraping down separated the magnetite from the slurry. The series of magnetic separation operations described above was repeated until no new magnetic substances were generated to separate the non-magnetic substances and the magnetic substances. The masses of the obtained non-magnetic and magnetic substances were measured, the silicon element was quantified by the above method, and the residual ratio and removal ratio of the silicon element were determined according to the above formula. Table 1 shows the results.
（実施例４）
実施例３と同様の操作で得られた燃焼飛灰７５０．０ｇを容量０．００３ｍ3のポリプロピレンボトル（瑞穂化成工業株式会社製、）に入れ、純水２．２５ｋｇを加え、２５質量％スラリー溶液とした。このスラリー溶液を攪拌後、１．４テスラの高勾配磁選機（日本エリーズマグネチックス株式会社製、Ｌ－４）に投入し、磁選を行った。高勾配磁選機下部より、マトリックスを通過した非磁着物を回収し、マトリックスに付着していた磁着物は、高勾配磁選機の磁場を切った後に、マトリックスを純水で洗浄し、回収した。得られた非磁着物および磁着物の質量を測定し、上記方法によりケイ素元素を定量し、上記式に従い、ケイ素元素の残存率および除去率を求めた。結果を表１に示す。
(Example 4)
750.0 g of combustion fly ash obtained by the same operation as in Example 3 was placed in a polypropylene bottle with a capacity of 0.003 m 3 (manufactured by Mizuho Chemical Industry Co., Ltd.), and 2.25 kg of pure water was added to make a 25% by mass slurry. solution. After stirring the slurry solution, it was placed in a 1.4 Tesla high gradient magnetic separator (L-4, manufactured by Eriez Magnetics Japan Co., Ltd.) for magnetic separation. Non-magnetic substances that passed through the matrix were collected from the lower part of the high gradient magnetic separator, and magnetic substances adhering to the matrix were collected by washing the matrix with pure water after turning off the magnetic field of the high gradient magnetic separator. The masses of the obtained non-magnetic and magnetic substances were measured, the silicon element was quantified by the above method, and the residual ratio and removal ratio of the silicon element were determined according to the above formula. Table 1 shows the results.
（実施例５、比較例１～３）
高勾配磁選機の磁力を表１に記載の通りに変更した点以外は実施例４と同様の操作を行い、ケイ素元素の残存率および除去率を求めた。結果を表１に示す。
(Example 5, Comparative Examples 1 to 3)
The same operation as in Example 4 was performed except that the magnetic force of the high gradient magnetic separator was changed as shown in Table 1, and the residual rate and removal rate of the silicon element were determined. Table 1 shows the results.
実施例４にて得られた磁着物および非磁着物を、ＳＥＭ－ＥＤＸ（日本電子株式会社、ＪＳＭ－７８００Ｆ Ｐｒｉｍｅ）にてケイ素、鉄、ニッケルの測定を行った。図１に磁着物の結果を、図２に非磁着物の結果を示す。
図１および２より、磁着物ではケイ素が鉄、ニッケルの近傍に存在すること、一方で非磁着物ではケイ素が鉄、ニッケルの近傍には存在しないことが判る。
The magnetic and non-magnetic materials obtained in Example 4 were measured for silicon, iron, and nickel by SEM-EDX (JEOL Ltd., JSM-7800F Prime). FIG. 1 shows the results for magnetic deposits, and FIG. 2 shows the results for non-magnetic deposits.
From FIGS. 1 and 2, it can be seen that silicon exists in the vicinity of iron and nickel in the magnetized material, while silicon does not exist in the vicinity of iron and nickel in the non-magnetic material.
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