JP2802906B2 - Wet treatment of heavy oil ash - Google Patents
Wet treatment of heavy oil ashInfo
- Publication number
- JP2802906B2 JP2802906B2 JP8032688A JP3268896A JP2802906B2 JP 2802906 B2 JP2802906 B2 JP 2802906B2 JP 8032688 A JP8032688 A JP 8032688A JP 3268896 A JP3268896 A JP 3268896A JP 2802906 B2 JP2802906 B2 JP 2802906B2
- Authority
- JP
- Japan
- Prior art keywords
- heavy oil
- wet
- oil ash
- water
- ash
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000295 fuel oil Substances 0.000 title claims description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 34
- 239000002245 particle Substances 0.000 claims description 34
- 229910052799 carbon Inorganic materials 0.000 claims description 33
- 238000010298 pulverizing process Methods 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- 238000002386 leaching Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 3
- 238000003672 processing method Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 32
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 27
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 18
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 18
- 235000011130 ammonium sulphate Nutrition 0.000 description 18
- 229910021529 ammonia Inorganic materials 0.000 description 12
- 239000000446 fuel Substances 0.000 description 10
- 239000002002 slurry Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 229910052602 gypsum Inorganic materials 0.000 description 7
- 239000010440 gypsum Substances 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- 238000005649 metathesis reaction Methods 0.000 description 5
- 150000003681 vanadium Chemical class 0.000 description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 4
- 235000011941 Tilia x europaea Nutrition 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000004571 lime Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical class [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000010344 co-firing Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 102200118166 rs16951438 Human genes 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
Landscapes
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Processing Of Solid Wastes (AREA)
- Carbon And Carbon Compounds (AREA)
- Liquid Carbonaceous Fuels (AREA)
Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【発明の属する技術分野】本発明は、重油焚きボイラー
（重油又は原油等を燃料とする火力発電所等に代表され
る。）から排出される重油灰を処理して分離回収した各
成分（又は生成物）を有効利用するための重油灰の湿式
処理方法に関する。BACKGROUND OF THE INVENTION The present invention relates to a fuel oil boiler (represented by a thermal power plant or the like using fuel oil or crude oil as a fuel). The present invention relates to a method for wet-treating heavy oil ash for effectively utilizing the product.
【０００２】[0002]
【従来の技術】火力発電所等から排出される重油灰は、
未燃カーボンが主体であるが、これに同伴する硫酸ミス
トを中和しカーボンダストの電気集塵特性を改善するた
めに注入されるアンモニア（ガス）により、比較的多量
（30〜50％) の硫安（詳しくは硫安と酸性硫安の混合
物）を含んでいる。2. Description of the Related Art Heavy oil ash discharged from thermal power plants, etc.
Although mainly unburned carbon, a relatively large amount (30 to 50%) of ammonia (gas) injected to neutralize the sulfuric acid mist that accompanies it and to improve the electric dust collection characteristics of carbon dust. Contains ammonium sulfate (more specifically, a mixture of ammonium sulfate and acidic ammonium sulfate).
【０００３】また、その他に燃料重油（成分）に由来す
るV,Ni,Fe,Si,Al,Ca,Mg,Na等からなる小量(7〜15％) の
灰分を含んでいる。[0003] In addition, it contains a small amount (7 to 15%) of ash composed of V, Ni, Fe, Si, Al, Ca, Mg, Na and the like derived from fuel heavy oil (component).
【０００４】従来より、この重油灰の処理方法として
は、そのまま袋詰めして廃棄する埋立処理やサイクロン
ファーネス，流動培焼炉，ロータリーキルン等による焼
却減容化処理が行われてきた。Conventionally, as a method for treating heavy oil ash, landfill treatment in which bags are packed and discarded as they are, and incineration volume reduction treatment using a cyclone furnace, a fluidized sintering furnace, a rotary kiln, or the like have been performed.
【０００５】ところで、大型火力発電所から排出される
重油灰量は、1000ＭＷ当たり4000〜6000ton/ｙと膨大で
ある。しかも電気集塵機（ＥＰ）捕集灰はかさ比重が
0.1〜0.2 ton/m3と非常に小さく、嵩張る。[0005] The amount of heavy oil ash discharged from large thermal power plants is enormous at 4000 to 6000 tons / y per 1000 MW. In addition, the ash collected by the electric dust collector (EP) has a bulk specific gravity.
Very small and 0.1~0.2 ton / m 3, bulky.
【０００６】したがって、産業廃棄物として埋立処理を
するとしても処分には多大な費用がかかり、また用地確
保が年々困難になって来ている。[0006] Therefore, even if landfill treatment is performed as industrial waste, disposal requires a great deal of cost, and it is becoming increasingly difficult to secure land every year.
【０００７】一方、焼却減容化処理においても、重油灰
中のカーボンは燃えにくくカロリーや組成変動が大きい
ので燃焼制御が難しいこと、多量の硫安が低温(280〜50
0 ℃）で分解し800 ℃以上になると酸化されNO2 濃度が
急増すること、後流の低温部(300℃前後) で再結合し付
着して腐食トラブルの原因になること、カーボンを燃焼
した残渣にV2O5,Fe2O3,Na2SO4 等を含みこれらが低融点
化合物を生成し800 〜900 ℃で溶着して腐食トラブル
（所謂バナジウム・アタック）の原因になること等の問
題をかかえている。On the other hand, even in the incineration volume reduction treatment, carbon in heavy oil ash is difficult to burn due to its low calorie and composition fluctuation, and it is difficult to control combustion.
Decomposed at 0 ℃) and oxidized at 800 ℃ or higher, the NO 2 concentration rapidly increased, recombined and adhered in the downstream low temperature part (around 300 ℃), causing corrosion problems, burning carbon Residues contain V 2 O 5 , Fe 2 O 3 , Na 2 SO 4, etc., which form low melting point compounds and are welded at 800-900 ° C. to cause corrosion problems (so-called vanadium attack). I have a problem.
【０００８】したがって、焼却設備は何れも冷気クエン
チや温水噴霧等で厳しく炉内温度をコントロールし、先
ず600 ℃で硫安を分解した後、800 ℃でゆるやかにカー
ボン燃焼をおこなっている。Therefore, all incinerators strictly control the furnace temperature by means of cold air quench, hot water spray or the like, first decompose ammonium sulfate at 600 ° C., and then slowly burn carbon at 800 ° C.
【０００９】上述したように重油灰中の付着硫安やバナ
ジウム塩等が未燃カーボンの有効利用や処理のネックに
なっていることから、湿式処理によりこれらを浸出分離
し、各々を有効利用する方法が進められている。As described above, the adhesion of ammonium sulfate and vanadium salt in heavy oil ash is a bottleneck in the effective use and treatment of unburned carbon. Is being promoted.
【００１０】例えば、特開平５−１５６２６８号ではＥ
Ｐ捕集灰を湿式処理して、得られたカーボンケーキ（含
水率20〜60％）はボイラー燃料重油に混合して混合燃料
とし、硫安を浸出した液には消石灰を加えアンモニアと
石膏を回収し、アンモニアは煙道に戻し再利用する方法
を提案している。For example, Japanese Patent Application Laid-Open No. 5-156268 discloses E
P-collected ash is wet-processed, and the obtained carbon cake (water content: 20-60%) is mixed with boiler fuel heavy oil to make a mixed fuel, and slaked lime is added to the liquid leached with ammonium sulfate to recover ammonia and gypsum Then, ammonia is proposed to be returned to the flue and reused.
【００１１】また、特開昭６０−１９０８６号及び特開
昭６０−４６９３０号では重油灰を湿式処理し、pH調
整、加熱、酸化等をおこないながらバナジウムを沈澱回
収し、残液には上記例と同様に消石灰を加えアンモニア
と石膏を回収しリサイクル利用している。なお、これら
の出願に係る処理方法はその後さらに改良され、重油灰
中の硫安を利用してバナジン酸アンモニウム化合物をつ
くり、その溶解温度特性を利用して効率的な浸出及び晶
析をこない、バナジウムを回収している。現在、5000to
n/ｙの実プラントが稼働しており、回収されたカーボン
ケーキはセメント工場の燃料として利用されている。In Japanese Patent Application Laid-Open Nos. 60-19086 and 60-46930, heavy oil ash is wet-processed, and vanadium is precipitated and recovered while performing pH adjustment, heating, oxidation and the like. As in the above, slaked lime is added to collect ammonia and gypsum for recycling. The treatment methods according to these applications have been further improved, and ammonium vanadate compounds have been produced using ammonium sulfate in heavy oil ash, and vanadium has not been efficiently leached and crystallized using its melting temperature characteristics. Has been collected. Currently 5000to
An actual n / y plant is in operation, and the recovered carbon cake is used as fuel for cement factories.
【００１２】[0012]
【発明が解決しようとする課題】こうしたなかで本発明
者らは、重油灰未燃カーボンの有効利用に関し、各種燃
料、製鋼用還元材、ゴム・プラスチック用フィラー等へ
の用途開拓に鋭意研究を重ねてきた。Under these circumstances, the present inventors have made intensive studies on the effective use of heavy oil and ash unburned carbon to find applications in various fuels, reducing materials for steelmaking, fillers for rubber and plastics, and the like. I have piled up.
【００１３】これらの用途には、先ず湿式処理し、硫安
やバナジウム塩等を分離する必要があり、さらに有用化
・合理化を進めてゆくには次のような技術解決課題があ
ることを明らかにしてきた。For these uses, it is necessary to first perform a wet treatment to separate ammonium sulfate, vanadium salts, etc. It is clear that there are the following technical solution issues for further utilization and rationalization. I've been.
【００１４】湿式処理し分離したカーボンケーキの含
水率は60〜65％と非常に高く乾燥費用が嵩む。したがっ
てその低減対策が望まれる。The water content of the wet-processed and separated carbon cake is as high as 60 to 65%, and the drying cost is high. Therefore, reduction measures are desired.
【００１５】ゴム・プラスチックス用充填材として用
いられる工業用カーボンブラックの粒子径は一般にシン
グルミクロンオーダーであり、重油灰未燃カーボンより
１オーダー小さい。したがってこれらに代替するために
はより微細化が要求される。The particle size of industrial carbon black used as a filler for rubber and plastics is generally of the order of a single micron, which is one order of magnitude smaller than that of heavy oil ash unburned carbon. Therefore, miniaturization is required to replace them.
【００１６】燃料材としての重油灰未燃カーボンは微
粉炭より燃焼性が悪い。（一部コークス化したものと考
えられる。）したがって微粉炭焚きボイラー等に混焼す
る場合に燃焼性の改善が要請される。Heavy oil ash unburned carbon as a fuel material has lower flammability than pulverized coal. (It is considered that the coke is partially coke.) Therefore, when co-firing in a pulverized coal-fired boiler or the like, improvement of flammability is required.
【００１７】[0017]
【課題を解決するための手段】上記課題を解決するため
に本発明は、重油灰を湿式処理して、不溶性のカーボン
と水溶性物質を分離し、その各々を回収して再生利用又
は廃棄処理するための重油灰の湿式処理方法において、
浸出工程又は固液分離工程の前処理として重油灰組成中
のカーボン粒子を微細化する粉砕工程を包含することを
特徴とするものである。SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention provides a method for wet-treating heavy oil ash to separate insoluble carbon and water-soluble substances, recovering each of them, and recycling or discarding them. In the wet processing method of heavy oil ash for
As a pretreatment of the leaching step or the solid-liquid separation step, a pulverizing step of pulverizing carbon particles in the heavy oil ash composition is included.
【００１８】[0018]
【発明の実施の形態】本発明は、重油灰の湿式処理にお
ける浸出工程又は固液分離工程の前処理として、重油灰
組成中の未燃カーボン粒子を微細化する粉砕工程を包含
し、その微細化の程度が未燃カーボン粒子の平均粒子径
を 0.5〜15μｍ範囲に制御するものである。後述するよ
うに２〜８μｍ範囲とされるのが好ましい。そして、未
燃カーボン粒子を微細化するための粉砕工程が湿式粉砕
処理又は乾式粉砕処理とされる。湿式粉砕処理は、固液
分離工程の前処理としておこなわれ、場合によっては、
浸出工程を包含するものであり、乾式粉砕処理は、固液
分離工程の前処理としておこなわれるものである。BEST MODE FOR CARRYING OUT THE INVENTION The present invention includes, as a pretreatment of a leaching step or a solid-liquid separation step in a wet treatment of heavy oil ash, a pulverizing step of pulverizing unburned carbon particles in a heavy oil ash composition. The degree of formation controls the average particle diameter of the unburned carbon particles in the range of 0.5 to 15 μm. As described later, the thickness is preferably in the range of 2 to 8 μm. Then, the pulverizing step for making the unburned carbon particles fine is a wet pulverizing treatment or a dry pulverizing treatment. The wet grinding treatment is performed as a pretreatment of the solid-liquid separation step, and in some cases,
It includes a leaching step, and the dry pulverization treatment is performed as a pretreatment of the solid-liquid separation step.
【００１９】ここで粉砕は、未燃カーボン粒子の含水率
を低下させるための機械的（物理的）な粉砕であって、
その作用は未燃カーボン粒子の保水機構を破壊するもの
である。Here, the pulverization is a mechanical (physical) pulverization for reducing the water content of the unburned carbon particles,
Its action is to destroy the water retention mechanism of the unburned carbon particles.
【００２０】すなわち、未燃カーボン粒子の性状は、平
均粒子径が20〜40μｍ，比表面積が10〜40m2/gであり、
同じ粒子径及び比表面積の一般粉粒体に比して含水率が
異常に大きいという特徴を有している。また、その粒子
形状は中空のゴルフボール状を呈する。〔重油又は原油
が燃焼過程で微細な液滴としてボイラー（火炉）内に噴
霧され、液滴の表面や内部の揮発分がぬけながら燃焼す
ることから、重油灰は燃え残ったカーボン（重油灰の主
成分）がポーラスな球状に結合したものとみられる。〕
そして、この中空部には水分（間隙水）を含むが、粒子
自体が小さいために一般的な固液分離操作では脱水でき
ず、上記比表面積の割には大きな含水率を示すものとな
っている。したがって、含水率を低下させるためには中
空粒子形状を破壊し、間隙水（内部包含水）を除去する
ことが有効である。That is, the properties of the unburned carbon particles are such that the average particle diameter is 20 to 40 μm and the specific surface area is 10 to 40 m 2 / g;
It has a feature that the moisture content is unusually large as compared with general powders having the same particle diameter and specific surface area. The particle shape is a hollow golf ball. [Heavy oil or crude oil is sprayed into the boiler (furnace) as fine droplets during the combustion process, and burns while the volatiles on the surface and inside of the droplets are removed. The main component) is considered to be bonded in a porous spherical shape. ]
Although this hollow portion contains water (interstitial water), it cannot be dehydrated by a general solid-liquid separation operation because the particles themselves are small, and shows a large water content for the above specific surface area. I have. Therefore, in order to reduce the water content, it is effective to destroy the hollow particle shape and remove pore water (internally contained water).
【００２１】なお、粒子径が含水率に及ぼす影響に関
し、一般的な粉粒体では、粉砕により微細化してその平
均粒子径を１オーダー小さくすると、比表面積は（粒子
形状によって多少異なるが）約10倍程度大きくなり、こ
れにともなって付着水（吸着水) も増大する。この点
は、重油灰の未燃カーボン粒子も同様であり（したがっ
て微細化粉砕において好適な平均粒子径の範囲を要請す
る。後述）、さらに結晶水（底質粒子内）や毛管水（底
質粒子の隣接部) を含むが、上記間隙水（内部包含水）
の除去によって含水率を３割程度低下させることができ
る。With respect to the effect of the particle size on the water content, when a general powder is refined by pulverization and the average particle size is reduced by one order, the specific surface area (although it varies slightly depending on the particle shape) is about It becomes about 10 times larger, and the attached water (adsorbed water) also increases accordingly. This point is the same for the unburned carbon particles of heavy oil ash (therefore, a range of an average particle diameter suitable for fine pulverization is required. As described later), crystallization water (in sediment particles) and capillary water (sediment water) are also required. (Adjacent part of particles)
, The water content can be reduced by about 30%.
【００２２】そこで、図面を参照して好適な実施態様を
説明する。図１はそのフローシートであり、ａが溶解
槽、ｂが湿式粉砕機、ｃが固液分離機、ｄが乾燥機、ｅ
が硫安濾液槽、ｆが石灰スラリー槽、ｇが硫安複分解反
応槽、ｈがアンモニア放散塔、ｉがアンモニア吸収塔、
ｊが石膏スラリー貯槽及びｋがアンモニア水貯槽であ
る。なお、数字符号は取り扱われる物質である。A preferred embodiment will now be described with reference to the drawings. FIG. 1 shows the flow sheet, wherein a is a dissolution tank, b is a wet pulverizer, c is a solid-liquid separator, d is a drier, and e is
Is an ammonium sulfate filtrate tank, f is a lime slurry tank, g is an ammonium sulfate metathesis reaction tank, h is an ammonia diffusion tower, i is an ammonia absorption tower,
j is a gypsum slurry storage tank and k is an ammonia water storage tank. In addition, a numerical code is a substance to be handled.
【００２３】まず、ＥＰ捕集灰（１）を溶解槽（ａ）で
補給水（６）あるいは固液分離機（ｃ）のケーキ洗浄液
（２）に溶解させ、回収アンモニア水（３）の一部を加
え、pH調整しながら硫安及びバナジウム塩等の水可溶性
物質を溶出する。溶解槽（ａ）は攪拌機付き混合溶解槽
でありＥＰ捕集灰（１）が液中に均一分散されればよ
く、溶解は３０分以内で十分である。First, EP collected ash (1) is dissolved in make-up water (6) or cake washing liquid (2) of solid-liquid separator (c) in dissolving tank (a). And elute water-soluble substances such as ammonium sulfate and vanadium salts while adjusting the pH. The dissolving tank (a) is a mixing dissolving tank with a stirrer, and the EP collection ash (1) may be uniformly dispersed in the liquid, and dissolution within 30 minutes is sufficient.
【００２４】次に、溶解液（４）を湿式粉砕機（ｂ）に
送って懸濁している未燃カーボン粒子を粉砕する。湿式
粉砕機（ｂ）は、所定の粒度まで１時間以内で粉砕可能
な湿式振動ミル、湿式ボールミル、湿式タワーミル等で
よい。Next, the solution (4) is sent to a wet pulverizer (b) to pulverize the suspended unburned carbon particles. The wet pulverizer (b) may be a wet vibration mill, a wet ball mill, a wet tower mill, or the like that can pulverize to a predetermined particle size within one hour.
【００２５】ただし、この粉砕の程度（粒度範囲）は重
要で、粉砕し過ぎても不足してもいけない。過度の粉砕
（微細化）は本発明の含水率低減効果において逆効果と
なり、粉砕動力費の上昇や後流の濾過性能の悪化を招く
ため、湿式粉砕機の機種や性能の応じて所定の粒度範囲
（平均粒子径で0.5 〜15μｍ範囲より好ましくは２〜８
μｍ範囲）に制御すべく粉砕時間や粉砕機の粉砕強度を
調整することが重要である。なお、前段の溶解槽（ａ）
での硫安及びバナジウム塩等の一部金属塩を溶出する処
理は湿式粉砕機（ｂ）においても機能的に可能なので、
機種によってＥＰ捕集灰（１）を直接安定供給できる場
合には、上記溶解槽（ａ）を省略してもよい。However, the degree of this pulverization (particle size range) is important, and it should not be too much or not enough. Excessive pulverization (micronization) has an adverse effect on the water content reduction effect of the present invention, and causes an increase in pulverization power cost and deterioration of the downstream filtration performance. Range (average particle size in the range of 0.5 to 15 μm, more preferably 2 to 8 μm)
It is important to adjust the pulverization time and the pulverization strength of the pulverizer in order to control the pulverization time in the range of μm. The former dissolution tank (a)
Since the treatment for eluting some metal salts such as ammonium sulfate and vanadium salt in the process is functionally possible even in the wet mill (b),
If EP collecting ash (1) can be directly and stably supplied depending on the model, the dissolving tank (a) may be omitted.
【００２６】所定粒度まで粉砕されたスラリー（５）を
固液分離機（ｃ）に送り、カーボンと硫安を含む濾液と
に分離する。回収されたカーボンケーキ（７）は、補給
水（６）で十分洗浄し、必要に応じて乾燥機（ｄ）によ
り乾燥し、燃料、フィラー、還元材等として再利用に供
する。The slurry (5) pulverized to a predetermined particle size is sent to a solid-liquid separator (c), and separated into carbon and a filtrate containing ammonium sulfate. The collected carbon cake (7) is sufficiently washed with make-up water (6), and if necessary, dried with a dryer (d), and is reused as a fuel, a filler, a reducing material, and the like.
【００２７】一方、硫安を含む分離濾液（８）は、従来
技術と同様の手法で硫安を複分解させるための複分解反
応槽（ｇ）に送り、石灰スラリー（12）を加え複分解反
応させ、アンモニアガス（13）と石膏スラリー（14）を
回収する。On the other hand, the separated filtrate (8) containing ammonium sulfate is sent to a metathesis reaction tank (g) for metathesis of ammonium sulfate in the same manner as in the prior art, and a lime slurry (12) is added to cause a metathesis reaction, and ammonia gas is added. Collect (13) and gypsum slurry (14).
【００２８】複分解反応槽（ｇ）を出た石膏スラリー
（14）は溶解アンモニアを含むので、アンモニア放散塔
（ｈ）で空気（15）を吹き込みアンモニアガス（16）を
放散させ、アンモニア吸収塔（ｉ）で水（６）に吸収し
15％程度の濃度のアンモニア水（３）として回収する。Since the gypsum slurry (14) that has left the metathesis reaction tank (g) contains dissolved ammonia, air (15) is blown into the ammonia stripping tower (h) to diffuse ammonia gas (16), and the ammonia absorbing tower (14). absorbed in water (6) in i)
It is recovered as aqueous ammonia (3) having a concentration of about 15%.
【００２９】アンモニアを放散させた石膏スラリー（1
7）には、未反応の石灰が小量含まれているので、発電
所の排煙脱硫装置に送り一括処理する。Gypsum slurry (1
Since 7) contains a small amount of unreacted lime, it is sent to the flue gas desulfurization unit of the power plant for batch processing.
【００３０】また、回収されたアンモニア水（３）は、
一部を溶解槽（ａ）のpH調整に使用する他は発電所に送
り、煙道へのアンモニア注入用として再利用する。The recovered ammonia water (3)
Others are used for adjusting the pH of the dissolution tank (a), and the others are sent to the power plant and reused for injecting ammonia into the flue.
【００３１】[0031]
【００３２】本発明の一実施例を図表を参照して以下説
明する。An embodiment of the present invention will be described below with reference to the drawings.
【００３３】火力発電所重油専焼ボイラーから排出され
た重油灰を、振動ミル（川崎重工業（株）製；型式 T-2
50, モーター回転数 800rpm ）により固形分濃度10wt％
で湿式粉砕し、そのスラリーを真空濾過・洗浄し、得ら
れたカーボンケーキの含水率と粒度（平均粒子径）を測
定した。測定結果を表１、及び図２に示す。The heavy oil ash discharged from the heavy oil boiler for the thermal power plant is converted into a vibration mill (manufactured by Kawasaki Heavy Industries, Ltd .; Model T-2).
50, motor rotation speed 800rpm), solid content concentration 10wt%
And the slurry was vacuum filtered and washed, and the water content and particle size (average particle size) of the obtained carbon cake were measured. The measurement results are shown in Table 1 and FIG.
【００３４】[0034]
【表１】 [Table 1]
【００３５】結果に示すように、約１時間の粉砕で、63
％含水率を43％含水率まで低減できた。ここで、40％台
の含水率の低減効果を有効とみたとき、その平均粒子径
は 0.5〜15μｍ範囲である。それ以上のサブミクロンへ
の粉砕は、含水率の低減効果がなく（かえって上昇す
る）、所要動力費が嵩み、濾過も困難になるので、逆効
果であるといえる。なお、本発明方法に関しては未燃カ
ーボンの保水機構（中空粒子形状）を破壊できれば目的
（含水率の低減）が達成されるのであり、種々の実績
（記載省略）を考慮すると、より好ましくは２〜８μｍ
範囲を推奨することができる。As shown in the results, after grinding for about 1 hour, 63
% Water content could be reduced to 43% water content. Here, when the effect of reducing the water content on the order of 40% is considered to be effective, the average particle size is in the range of 0.5 to 15 μm. Further pulverization to a submicron has no effect of reducing the water content (instead of increasing), increases the required power cost, and makes filtration difficult. In the method of the present invention, if the water retention mechanism (hollow particle shape) of unburned carbon can be destroyed, the object (reduction of water content) is achieved. ~ 8 μm
A range can be recommended.
【００３６】[0036]
【発明の効果】本発明は以上の構成よりなるものであ
り、これによれば（１）含水率の低減と浸出・洗浄処理
の効率アップ、（２）燃焼性（着火及び燃え切り）の向
上、及び（３）回収したカーボンケーキの用途拡大が可
能である。According to the present invention, the present invention has the above-mentioned structure, and according to the present invention, it is possible to (1) reduce the water content and increase the efficiency of the leaching / cleaning treatment, and (2) improve the flammability (ignition and burnout). And (3) the use of the recovered carbon cake can be expanded.
【００３７】具体的な項目について以下列挙する。 含水率の低減効果によりカーボンケーキの乾燥コスト
が低減でき、用途によっては乾燥工程の省略も可能であ
り、総じて経済効果が期待できる。 含水率の低減効果によりカーボンケーキの付着水に含
まれる硫安等の溶質量も減少するので、浸出分離効率が
向上する。 微細化（粉砕）によりバナジウム塩等可溶性金属塩の
浸出効率が向上するとともに洗浄効率が向上する。 微細化（粉砕）により燃焼性（着火及び燃え切り）が
向上し、ボイラー燃料として再利用可能である。 微細化（３μｍ以下）及び浸出・洗浄効率の向上にと
もない工業用カーボンブラックに代替可能な材料化（特
にゴム・プラスチックス用充填材等としてカーボンケー
キの用途開拓）が期待できる。Specific items are listed below. Due to the effect of reducing the water content, the drying cost of the carbon cake can be reduced, and depending on the application, the drying step can be omitted, and overall economic effects can be expected. Due to the effect of reducing the water content, the dissolved mass of ammonium sulfate and the like contained in the water adhering to the carbon cake is also reduced, so that the leaching separation efficiency is improved. The miniaturization (pulverization) improves the leaching efficiency of a soluble metal salt such as a vanadium salt and the cleaning efficiency. Combustibility (ignition and burn-out) is improved by miniaturization (pulverization), and the fuel can be reused as boiler fuel. Along with miniaturization (3 μm or less) and improvement of leaching and washing efficiency, it is expected that a material that can be substituted for industrial carbon black (especially the use of carbon cake as a filler for rubber and plastics, etc.) will be developed.
【図１】本発明の実施の形態を説明するためのフローシ
ートである。FIG. 1 is a flow sheet for explaining an embodiment of the present invention.
【図２】本発明の一実施例で得られたカーボンケーキの
測定結果である含水率 vs.粉砕時間を示すデータプロッ
トである。FIG. 2 is a data plot showing water content vs. grinding time, which is a measurement result of a carbon cake obtained in one example of the present invention.
ａ 溶解槽 ｂ 湿式粉砕機 ｃ 固液分離機 ｄ 乾燥機 ｅ 硫安濾液槽 ｆ 石灰スラリー槽 ｇ 硫安複分解反応槽 ｈ アンモニア放散塔 ｉ アンモニア吸収塔 ｊ 石膏スラリー貯槽 ｋ アンモニア水貯槽 a dissolution tank b wet pulverizer c solid-liquid separator d drier e ammonium sulfate filtrate tank f lime slurry tank g ammonium sulfate double decomposition reaction tank h ammonia emission tower i ammonia absorption tower j gypsum slurry storage tank k ammonia water storage tank
───────────────────────────────────────────────────── フロントページの続き (72)発明者 東 則明 広島県広島市中区小町４番33号 中国電 力株式会社内 (72)発明者 福田 克己 広島県広島市西区南観音町二丁目９番46 −602号 (72)発明者 北村 信博 広島県廿日市市大東６−33−603号 (72)発明者 松本 和大 広島県広島市西区草津南二丁目８−34 (72)発明者 石村 和彦 広島県広島市佐伯区八幡東一丁目29−37 −９ (58)調査した分野(Int.Cl.6，ＤＢ名) C10G 31/00 B09B 5/00 C01B 31/02──────────────────────────────────────────────────続 き Continuing on the front page (72) Noriaki Higashi 4-33 Komachi, Naka-ku, Hiroshima City, Hiroshima Prefecture Inside Chugoku Electric Power Co., Inc. (72) Katsumi Fukuda 2--9 Minamikanoncho, Nishi-ku, Hiroshima City, Hiroshima Prefecture 46-602 (72) Inventor Nobuhiro Kitamura 6-33-603 Daito, Hatsukaichi City, Hiroshima Prefecture (72) Inventor Kazuhiro Matsumoto 2-34 Kusatsu Minami 2-chome, Nishi-ku, Hiroshima City, Hiroshima Prefecture (72) Inventor Kazuhiko Ishimura Hiroshima (58) Field surveyed (Int. Cl. 6 , DB name) C10G 31/00 B09B 5/00 C01B 31/02
Claims (4)
ーボン（粒子）と可溶性物質を分離し、その各々を回収
して再生利用又は廃棄処理するための重油灰の湿式処理
方法において、浸出工程又は固液分離工程の前処理とし
て重油灰組成中の未燃カーボン粒子を微細化する粉砕工
程を包含することを特徴とする重油灰の湿式処理方法。1. A method of wet-treating heavy oil ash for wet-treating heavy oil ash to separate insoluble unburned carbon (particles) and a soluble substance, recovering each of them, and recycling or discarding them. A wet processing method for heavy oil ash, comprising a pulverizing step of pulverizing unburned carbon particles in a heavy oil ash composition as a pretreatment of a leaching step or a solid-liquid separation step.
均粒子径を 0.5〜15μｍ範囲に制御することを特徴とす
る請求項１記載の重油灰の湿式処理方法。2. The method according to claim 1, wherein the average particle size of the unburned carbon particles in the pulverizing step is controlled in the range of 0.5 to 15 μm.
２記載の重油灰の湿式処理方法。3. The method according to claim 1, wherein the pulverizing step is wet pulverization.
２記載の重油灰の湿式処理方法。4. The method according to claim 1, wherein the pulverizing step is dry pulverization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8032688A JP2802906B2 (en) | 1996-01-25 | 1996-01-25 | Wet treatment of heavy oil ash |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8032688A JP2802906B2 (en) | 1996-01-25 | 1996-01-25 | Wet treatment of heavy oil ash |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09202885A JPH09202885A (en) | 1997-08-05 |
| JP2802906B2 true JP2802906B2 (en) | 1998-09-24 |
Family
ID=12365816
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8032688A Expired - Fee Related JP2802906B2 (en) | 1996-01-25 | 1996-01-25 | Wet treatment of heavy oil ash |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2802906B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4956910B2 (en) * | 2005-04-22 | 2012-06-20 | 宇部興産株式会社 | Method and apparatus for wet pulverization of incinerated ash |
| JP4931745B2 (en) * | 2007-09-10 | 2012-05-16 | 中国電力株式会社 | Heavy oil ash scattering suppression device |
-
1996
- 1996-01-25 JP JP8032688A patent/JP2802906B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09202885A (en) | 1997-08-05 |
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