JP4441225B2 - Exhaust gas treatment material, gas filter, and exhaust gas treatment method - Google Patents

Exhaust gas treatment material, gas filter, and exhaust gas treatment method Download PDF

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JP4441225B2
JP4441225B2 JP2003335055A JP2003335055A JP4441225B2 JP 4441225 B2 JP4441225 B2 JP 4441225B2 JP 2003335055 A JP2003335055 A JP 2003335055A JP 2003335055 A JP2003335055 A JP 2003335055A JP 4441225 B2 JP4441225 B2 JP 4441225B2
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exhaust gas
gas treatment
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実 盛岡
智 田中
治 町長
芳夫 青山
弘之 三五
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Denka Co Ltd
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Denki Kagaku Kogyo KK
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本発明は、ゴミ焼却等において発生する高温酸性ガスを固定化するための排ガス処理材、該排ガス処理材を成形することを特徴とするガスフィルター、及び該ガスフィルターを用いた排ガスの処理方法に関する。本発明における部や%は特に規定しない限り質量基準で示す。   The present invention relates to an exhaust gas treatment material for fixing high-temperature acidic gas generated in refuse incineration, etc., a gas filter characterized by molding the exhaust gas treatment material, and an exhaust gas treatment method using the gas filter . Unless otherwise specified, parts and% in the present invention are shown on a mass basis.

大気汚染等の環境問題が深刻化している。ゴミ焼却炉等により発生する酸性ガス、例えば、塩素ガス、塩化水素ガス、亜硫酸ガス、次亜硫酸ガス等の排ガスの大気中への放出は厳しく制限されている。酸性ガスは、設備の腐食を促進するばかりでなく、酸性雨やダイオキシン生成の原因となるといわれている。   Environmental problems such as air pollution are becoming more serious. Release of exhaust gases such as chlorine gas, hydrogen chloride gas, sulfurous acid gas, and hyposulfite gas generated in a garbage incinerator or the like into the atmosphere is severely restricted. It is said that acid gas not only promotes corrosion of equipment but also causes acid rain and dioxin generation.

排ガスの処理材としては、水酸化カルシウムを用いる方法や(特許文献1,2等参照)、融点の比較的高いハイドロソーダライトを用いる方法(特許文献3,4等参照)、カルシウムアルミネートやその水和物を用いる方法(特許文献5,6等参照)等が提案されている。   As a treatment material for exhaust gas, a method using calcium hydroxide (see Patent Documents 1 and 2, etc.), a method using hydrosodalite having a relatively high melting point (see Patent Documents 3 and 4 etc.), calcium aluminate and its Methods using hydrates (see Patent Documents 5 and 6, etc.) have been proposed.

特開平05-261244号公報Japanese Patent Laid-Open No. 05-261244 特開平06-108034号公報JP 06-108034 A 特開平10-216510号公報Japanese Patent Laid-Open No. 10-216510 特開平11-267446号公報Japanese Patent Laid-Open No. 11-267446 特開平08-299752号公報Japanese Patent Laid-Open No. 08-299752 特開平08-309145号公報Japanese Unexamined Patent Publication No. 08-309145

排ガス処理材、ガスフィルター、及びそれらを用いた排ガスの処理方法を提供する。   An exhaust gas treatment material, a gas filter, and an exhaust gas treatment method using them are provided.

本発明は、4CaO・Al2O3・Fe2O3にSiO25%添加し溶融後に急冷して得た非晶質のカルシウムアルミノフェライトを含有する排ガス処理材であり、該排ガス処理材を成形することを特徴とするガスフィルターの製造方法であり、該排ガス処理材及び/又は該ガスフィルターを用いることを特徴とする排ガスの処理方法である。 The present invention is an exhaust gas treatment material containing amorphous calcium aluminoferrite obtained by adding 5% SiO 2 to 4CaO · Al 2 O 3 · Fe 2 O 3 and quenching after melting, and the exhaust gas treatment material Is a method for producing a gas filter, wherein the exhaust gas treatment material and / or the gas filter is used.

本発明の排ガス処理材は、塩化水素とSOXの双方の酸性ガスの固定化能力に優れ、排ガス処理材に酸性ガスが固定化された状態の融点が高く、1,300℃程度の高い温度領域まで酸性ガスを固定化することができ、焼却設備の腐食防止、酸性雨の発生防止、ダイオキシン生成の抑制等に有効である。 The exhaust gas treatment material of the present invention is excellent in the ability to immobilize both hydrogen chloride and SO X acid gas, has a high melting point in the state where the acid gas is immobilized on the exhaust gas treatment material, and has a high temperature range of about 1,300 ° C. It can fix acid gas and is effective in preventing corrosion of incinerators, preventing acid rain, and suppressing dioxin production.

カルシウムアルミノフェライトとは、CaO-Al2O3-Fe2O3系化合物を総称するものであり、CaOをC、Al2O3をA、Fe2O3をFで表したとき、例えば、C4AFと表される4CaO・Al2O3・Fe2O3、C6A2Fと表される6CaO・2Al2O3・Fe2O3、C6AF2と表される6CaO・Al2O3・2Fe2O3等が挙げられる。これらの結晶相は連続固溶体を形成するとも言われている。CaO-Al2O3-Fe2O3系化合物は、結晶質又は非晶質のいずれも使用可能である。 Calcium aluminoferrite is a generic term for CaO-Al 2 O 3 -Fe 2 O 3 compounds, and when CaO is represented by C, Al 2 O 3 by A, and Fe 2 O 3 by F, for example, 4CaO ・ Al 2 O 3・ Fe 2 O 3 expressed as C 4 AF, 6CaO ・ 2Al 2 O 3・ Fe 2 O 3 expressed as C 6 A 2 F, 6CaO ・ expressed as C 6 AF 2 Al 2 O 3 .2Fe 2 O 3 and the like can be mentioned. These crystalline phases are also said to form continuous solid solutions. As the CaO—Al 2 O 3 —Fe 2 O 3 series compound, either crystalline or amorphous can be used.

カルシウムアルミノフェライトは様々な組成を有するが、処理する排ガスの組成に応じて組成を変えることが好ましい。排ガス中の塩化水素濃度が高い場合には、Fe2O3含有量の高い6CaO・Al2O3・2Fe2O3を選定することが好ましく、排ガス中の亜硫酸ガスや次亜硫酸ガス等のSOX含有量が高い場合には、Al2O3含有量の高い6CaO・2Al2O3・Fe2O3を選定することが好ましい。 Although calcium aluminoferrite has various compositions, it is preferable to change the composition according to the composition of the exhaust gas to be treated. When the hydrogen chloride concentration in the exhaust gas is high, it is preferable to select 6CaO · Al 2 O 3 · 2Fe 2 O 3 having a high Fe 2 O 3 content, and SO 2 such as sulfurous acid gas or hyposulfite gas in the exhaust gas. when X content is high, it is preferable to select Al 2 O 3 higher content 6CaO · 2Al 2 O 3 · Fe 2 O 3.

カルシウムアルミノフェライトは、CaO原料、Al2O3原料、及びFe2O3原料を熱処理して得られる。CaO原料は、例えば、石灰石や貝殻等の炭酸カルシウム、消石灰等の水酸化カルシウム、生石灰等の酸化カルシウム等を挙げることができる。Al2O3原料としては、例えば、ボーキサイト、アルミドロス、及びアルミ残灰等を挙げることができる。Fe2O3原料としては、例えば、圧延スケールや各種のカラミと呼ばれる産業副産物、鉄粉、酸化鉄(II)、酸化鉄(III)、マグネタイト等が挙げられる。 Calcium aluminoferrite is obtained by heat-treating a CaO raw material, an Al 2 O 3 raw material, and an Fe 2 O 3 raw material. Examples of the CaO raw material include calcium carbonate such as limestone and shells, calcium hydroxide such as slaked lime, calcium oxide such as quick lime, and the like. Examples of the Al 2 O 3 raw material include bauxite, aluminum dross, and aluminum residual ash. Examples of the Fe 2 O 3 raw material include rolling by-products and various industrial by-products called calami, iron powder, iron (II) oxide, iron (III) oxide, and magnetite.

カルシウムアルミノフェライトを工業的に得る場合、不純物が含まれることがある。例えば、SiO2、MgO、TiO2、MnO、Na2O、K2O、Li2O、S、P2O5、及びF等が挙げられる。 When calcium aluminoferrite is obtained industrially, impurities may be contained. For example, SiO 2, MgO, TiO 2 , MnO, Na 2 O, K 2 O, Li 2 O, S, like P 2 O 5, and F or the like.

これらの不純物が含まれる化合物として、CaO・2Al2O3やCaO・Al2O3や12CaO・7Al2O3や11CaO・7Al2O3・CaF2や3CaO・Al2O3や3CaO・3Al2O3・CaSO4等のカルシウムアルミネート類、CaO・Fe2O3や2CaO・Fe2O3等のカルシウムフェライト、ゲーレナイト2CaO・Al2O3・SiO2やアノーサイトCaO・Al2O3・2SiO2等のカルシウムアルミノシリケート、メルビナイト3CaO・MgO・2SiO2やアケルマナイト2CaO・MgO・2SiO2やモンチセライトCaO・MgO・SiO2等のカルシウムマグネシウムシリケート、トライカルシウムシリケート3CaO・SiO2やダイカルシウムシリケート2CaO・SiO2やランキナイト3CaO・2SiO2やワラストナイトCaO・SiO2等のカルシウムシリケート、及びリューサイト(K2O、Na2O)・Al2O3・SiO2等が挙げられる。これらの相が結晶質又は非晶質の状態で混在しても良い。 As compounds in which these impurities are contained, CaO · 2Al 2 O 3 and CaO · Al 2 O 3 and 12CaO · 7Al 2 O 3 and 11CaO · 7Al 2 O 3 · CaF 2 or 3CaO · Al 2 O 3 and 3CaO · 3Al Calcium aluminates such as 2 O 3 and CaSO 4 , calcium ferrites such as CaO and Fe 2 O 3 and 2CaO and Fe 2 O 3 , gelenite 2CaO and Al 2 O 3 and SiO 2, and anorthite CaO and Al 2 O 3 · 2SiO 2 and calcium aluminosilicate, Merubinaito 3CaO · MgO · 2SiO 2 and Akerumanaito 2CaO · MgO · 2SiO 2 and Monte celite CaO · MgO · SiO 2 such as calcium magnesium silicate, tri-calcium silicate 3CaO · SiO 2 and Dicalcium silicate 2CaO · SiO 2 and rankinite night 3CaO · 2SiO 2 and wollastonite CaO · SiO 2 such as calcium silicate, and leucite (K 2 O, Na 2 O ) · Al 2 O 3 · SiO 2 and the like. These phases may be mixed in a crystalline or amorphous state.

本発明の排ガス処理材は、酸化カルシウム、水酸化カルシウム、炭酸カルシウムのうちの1種又は2種以上(以下「酸化カルシウム等」という)を併用しても良い。酸化カルシウム等を併用することにより、高温酸性ガスの吸蔵温度範囲を広くすることが可能である。カルシウムアルミノフェライトは1,000℃を超える高温での酸性ガス吸蔵特性に優れる一方で、500℃以下の比較的低い温度領域における酸性ガスの吸蔵特性が乏しいが、酸化カルシウム等を併用することにより、500℃以下の温度領域から1,300℃程度の非常に高い温度領域にわたって酸性ガスを吸蔵して固定化することが可能となる。酸化カルシウム等は、酸性ガスとの反応性の観点や比較的低い温度領域での酸性ガス固定化の観点から、水酸化カルシウム及び/又は酸化カルシウムが好ましく、水酸化カルシウムが最も好ましい。   The exhaust gas treatment material of the present invention may be used in combination with one or more of calcium oxide, calcium hydroxide, and calcium carbonate (hereinafter referred to as “calcium oxide and the like”). By using calcium oxide or the like together, it is possible to widen the storage temperature range of the high-temperature acidic gas. Calcium aluminoferrite has excellent acid gas storage characteristics at temperatures exceeding 1,000 ° C, while it has poor acid gas storage characteristics in a relatively low temperature range of 500 ° C or less. It becomes possible to occlude and fix the acidic gas over the very high temperature range of about 1,300 ° C. from the following temperature range. Calcium oxide and the like are preferably calcium hydroxide and / or calcium oxide, and most preferably calcium hydroxide, from the viewpoint of reactivity with acidic gas and fixation of acidic gas in a relatively low temperature range.

カルシウムアルミノフェライトと酸化カルシウム等の使用割合は特に限定されるものではないが、カルシウムアルミノフェライト及び酸化カルシウム等からなる排ガス処理材100部中、カルシウムアルミノフェライトの配合量は60〜100部が好ましく、70〜90部がより好ましい。カルシウムアルミノフェライト配合量が少ないと800℃以上の高温領域での酸性ガス吸蔵効果が不足する場合や、排ガス処理材が酸性ガスを吸収した後に溶融して焼却設備内に散在し、設備を腐食させる場合がある。500℃以下の比較的低い温度での酸性ガス吸蔵を目的とする場合、酸化カルシウム等を併用することが好ましい。カルシウムアルミノフェライトと酸化カルシウム等を併用することにより、幅広い温度領域において、優れた酸性ガス固定化能力を発揮する排ガス処理材となる。   The use ratio of calcium aluminoferrite and calcium oxide is not particularly limited, but in 100 parts of the exhaust gas treatment material consisting of calcium aluminoferrite and calcium oxide, the amount of calcium aluminoferrite is preferably 60 to 100 parts, More preferred is 70 to 90 parts. If the amount of calcium aluminoferrite is low, the effect of occluding the acidic gas in the high temperature range of 800 ° C or higher is insufficient, or the exhaust gas treatment material melts after absorbing the acidic gas and is scattered in the incineration equipment, corroding the equipment. There is a case. When the purpose is to store an acidic gas at a relatively low temperature of 500 ° C. or lower, it is preferable to use calcium oxide or the like in combination. By using calcium aluminoferrite and calcium oxide together, it becomes an exhaust gas treatment material that exhibits excellent acid gas fixing ability in a wide temperature range.

本発明では排ガス処理材料として、カルシウムアルミネート類、カルシウムフェライト類、カルシウムアルミノシリケート類、各種ポルトランドセメント、石灰石粉末等を混合したフィラーセメント、都市ゴミ焼却灰や下水汚泥焼却灰を原料として製造された環境調和型セメント(エコセメント)、高炉水砕スラグ、高炉徐冷スラグ、フライアッシュ、転炉スラグ、電気炉還元期スラグ、電気炉酸化期スラグ、パルプスラッジ焼却灰、下水汚泥焼却灰、都市ゴミ焼却灰、及び溶融スラグ等の各種粉末、上記の各種粉末に含まれる水硬性材料や潜在水硬性物質やポゾラン物質が水和して生成するあらゆる水和物類、アパタイト類、ゼオライト類、酸化マグネシウムや水酸化マグネシウムやドロマイトやハイドロタルサイト類等のマグネシウム化合物、活性炭等の炭素質物質、廃ガラス粉末、生コンスラッジ、並びに再生骨材を製造する際に発生するダストである再生微粉末等のうちの1種又は2種以上を、本発明の目的を実質的に阻害しない範囲で併用可能である。   In the present invention, as an exhaust gas treatment material, calcium aluminates, calcium ferrites, calcium aluminosilicates, various portland cements, filler cement mixed with limestone powder, municipal waste incineration ash and sewage sludge incineration ash were produced as raw materials. Environmentally friendly cement (eco-cement), granulated blast furnace slag, blast furnace slow-cooled slag, fly ash, converter slag, electric furnace reduction slag, electric furnace oxidation slag, pulp sludge incineration ash, sewage sludge incineration ash, municipal waste Various powders such as incinerated ash and molten slag, all hydrates, apatites, zeolites, magnesium oxide produced by hydration of hydraulic materials, latent hydraulic materials and pozzolanic materials contained in the above various powders And magnesium compounds such as magnesium hydroxide, dolomite and hydrotalcite 1 type or 2 or more types of carbonaceous materials such as activated carbon, waste glass powder, raw consludge, and regenerated fine powder that is dust generated when producing reclaimed aggregates are substantially used for the purpose of the present invention. Can be used as long as they are not hindered.

上記の排ガス処理材料は、本発明の排ガス処理材と併用しても良いし、別々に使用しても良い。一例を挙げると、融点が高い本発明の排ガス処理材を温度の高い場所(例えば、800〜1,200℃程度の場所)に設置し、融点の低い公知の排ガス処理材料、例えば、水酸化カルシウム等を温度の低い場所(例えば、300〜600℃程度の場所)に設置して併用することも可能である。このように複数の酸性ガス固定化処置を施すことは、ダイオキシン抑制等の観点から好ましい。   The above exhaust gas treatment material may be used in combination with the exhaust gas treatment material of the present invention, or may be used separately. For example, the exhaust gas treatment material of the present invention having a high melting point is installed in a place having a high temperature (for example, a place at about 800 to 1,200 ° C.), and a known exhaust gas treatment material having a low melting point, such as calcium hydroxide, is used. It is also possible to install and use it in a place with a low temperature (for example, a place of about 300 to 600 ° C.). Thus, it is preferable to perform a plurality of acid gas immobilization treatments from the viewpoint of dioxin suppression and the like.

本発明のカルシウムアルミノフェライトの粒度は特に限定されるものではないが、ブレーン比表面積値で2,000〜9,000cm2/gが好ましく、3,000〜6,000cm2/gがより好ましい。粗粒では高温酸性ガスの吸蔵効果が不足する場合があり、過剰に粉砕することは不経済性である。 The particle size of the calcium alumino ferrite of the present invention is not particularly limited, but is preferably 2,000~9,000cm 2 / g in Blaine specific surface area value, 3,000~6,000cm 2 / g is more preferable. In the case of coarse particles, the occlusion effect of high-temperature acidic gas may be insufficient, and excessive grinding is uneconomical.

本発明の排ガス処理材は、ガスフィルターとして利用しても良く、焼却物と共に焼却して使用しても良い。焼却物とともに排ガス処理材を焼却すると、焼却灰の量が増加し、廃棄物の量が増加するので、フィルターとして使用する方法が好ましい。本発明の排ガス処理材をガスフィルターとして利用すれば、使用済みのフィルターを回収して再生するか、又はセメント混和材等の他の用途へ転用することで、廃棄物の減容につながるので好ましい。   The exhaust gas treating material of the present invention may be used as a gas filter, or may be used after incineration with an incinerated product. When the exhaust gas treatment material is incinerated together with the incinerated material, the amount of incinerated ash increases and the amount of waste increases, so a method of using as a filter is preferable. If the exhaust gas treatment material of the present invention is used as a gas filter, it is preferable because the used filter is recovered and regenerated or diverted to other uses such as a cement admixture, leading to volume reduction of waste. .

ガスフィルターの製造方法としては、例えば、本発明の排ガス処理材を加圧成形する方法や、水硬性材料とともに水で混練して水和硬化させることで成形する方法等が挙げられる。   Examples of the method for producing a gas filter include a method for pressure-molding the exhaust gas treating material of the present invention, a method for molding by hydrating and curing with a hydraulic material together with water, and the like.

本発明の排ガス処理材は融点が高いものであり、酸性ガスが固定化された後の融点も高いものである。酸性ガス固定化後の融点が高いと、酸性ガス固定化後の排ガス処理材が分解して固定化した酸性ガスが再び放出されることがなく、焼却炉等の設備腐食を抑制することができ、フィルターが溶融せず交換が容易であるため、好ましい。   The exhaust gas treating material of the present invention has a high melting point, and also has a high melting point after the acidic gas is fixed. If the melting point after fixing the acid gas is high, the exhaust gas treatment material after fixing the acid gas will not be decomposed and the fixed acid gas will not be released again, and corrosion of equipment such as incinerators can be suppressed. The filter is preferable because it does not melt and can be easily replaced.

本発明の排ガス処理材やフィルターは、都市ゴミ焼却時に発生する酸性ガスの固定化だけでなく、塩素やイオウを含有する廃棄物である下水汚泥等の汚泥、生コンスラッジやパルプスラッジ等のスラッジを焼却する際に発生する酸性ガスの固定化等にも広範に利用可能である。   The exhaust gas treatment material and filter of the present invention not only immobilizes acid gas generated during incineration of municipal waste, but also sludge such as sewage sludge that is waste containing chlorine and sulfur, sludge such as raw sludge and pulp sludge. It can be widely used for fixing acid gas generated during incineration.

炭酸カルシウムと、酸化アルミニウム、及び酸化鉄(III)等を所定の割合で混合し、1,300℃で焼成してカルシウムアルミノフェライト(1)〜(4)を合成した。カルシウムアルミノフェライト(1)〜(4)は粉砕し、ブレーン比表面積5,000cm2/gの粉末とした。カルシウムアルミノフェライトと酸化カルシウム等を表1に示す割合で配合して排ガス処理材とし、該排ガス処理材を加圧成形して20kgのペレットとした。ペレットをガスフィルターとして用い、小型焼却炉の排ガス通路の温度が1,000℃±100℃となる位置に配設した。塩素含有量が約1%の都市ゴミ500kgと重油を主体とする廃油300kgからなるゴミを焼却し、焼却設備の煙道から排出される排ガスをガスフィルターで処理した。処理後のガス中の塩素とイオウを定量し、総排出塩素量及び総排出イオウ量とした。結果を表1に示す。比較例として、水酸化カルシウムのみを用いた場合や、ハイドロソーダライト、カルシウムアルミネート、カルシウムフェライトを用いた場合、排ガス処理材を用いなかった場合の結果も表1に併記した。 Calcium aluminoferrites (1) to (4) were synthesized by mixing calcium carbonate, aluminum oxide, iron (III) oxide, and the like at a predetermined ratio and firing at 1,300 ° C. Calcium aluminoferrites (1) to (4) were pulverized into powders having a brain specific surface area of 5,000 cm 2 / g. Calcium aluminoferrite and calcium oxide were blended in the proportions shown in Table 1 to obtain an exhaust gas treatment material, and the exhaust gas treatment material was pressure-molded to form 20 kg pellets. The pellet was used as a gas filter and was disposed at a position where the temperature of the exhaust gas passage of the small incinerator was 1,000 ° C. ± 100 ° C. Garbage consisting of 500 kg of municipal waste with a chlorine content of about 1% and 300 kg of waste oil mainly consisting of heavy oil was incinerated, and the exhaust gas discharged from the flue of the incineration facility was treated with a gas filter. Chlorine and sulfur in the gas after the treatment were quantified to obtain the total discharged chlorine amount and the total discharged sulfur amount. The results are shown in Table 1. As comparative examples, the results when only calcium hydroxide is used, when hydrosodalite, calcium aluminate, and calcium ferrite are used, and when no exhaust gas treatment material is used are also shown in Table 1.

<使用材料>
炭酸カルシウム :試薬1級
酸化鉄(III) :試薬1級
水酸化カルシウム :試薬1級
酸化カルシウム :試薬1級
カルシウムアルミノフェライト(1):4CaO・Al2O3・Fe2O3
カルシウムアルミノフェライト(2):6CaO・2Al2O3・Fe2O3
カルシウムアルミノフェライト(3):6CaO・Al2O3・2Fe2O3
カルシウムアルミノフェライト(4):カルシウムアルミノフェライト(1)の4CaO・Al2O3・Fe2O3にSiO2を5%添加し、1,650℃で溶融した後に急冷して得た、非晶質の4CaO・Al2O3・Fe2O3
ハイドロソーダライト:カオリンと水酸化ナトリウム水溶液を3対10のモル比で混合し、加熱機に入れ、100℃で10時間熱処理した後、固液分離、洗浄、乾燥して合成した。
<Materials used>
Calcium carbonate: Reagent primary iron oxide (III): Reagent primary calcium hydroxide: Reagent primary calcium oxide: Reagent primary calcium aluminoferrite (1): 4CaO · Al 2 O 3 · Fe 2 O 3
Calcium aluminoferrite (2): 6CaO ・ 2Al 2 O 3・ Fe 2 O 3
Calcium aluminoferrite (3): 6CaO ・ Al 2 O 3・ 2Fe 2 O 3
Calcium aluminoferrite (4): 5% SiO 2 added to 4CaO · Al 2 O 3 · Fe 2 O 3 in calcium aluminoferrite (1), melted at 1,650 ° C, and then rapidly cooled to obtain amorphous 4CaO ・ Al 2 O 3・ Fe 2 O 3 .
Hydrosodalite: Kaolin and sodium hydroxide aqueous solution were mixed at a molar ratio of 3 to 10, placed in a heater, heat-treated at 100 ° C. for 10 hours, solid-liquid separation, washing and drying to synthesize.

<測定方法>
排ガスの総排出塩素量及び総排出イオウ量:焼却設備から排出される排ガスを各ガスフィルターで処理し、ガスフィルターを通過したガスを水酸化ナトリウム水溶液へ通して中和し、水酸化ナトリウム水溶液に含まれる塩化水素ガスやSOXを塩素イオンや硫酸イオン等に変換した後、溶液中に溶け込んだ各種塩素イオンや各種イオウイオン等の量をイオンクロマトグラフィーにより定量し、その総量を求めた。
<Measurement method>
Total exhaust chlorine and exhaust sulfur: The exhaust gas discharged from the incineration facility is treated with each gas filter, and the gas that has passed through the gas filter is neutralized by passing it through an aqueous sodium hydroxide solution. After the hydrogen chloride gas and SO X contained in the solution were converted to chlorine ions, sulfate ions, etc., the amounts of various chlorine ions and various sulfur ions dissolved in the solution were quantified by ion chromatography, and the total amount was obtained.

Figure 0004441225
注:実験No.1-13、1-14、1-15の*印はフィルターが溶融・散在。
Figure 0004441225
Note: * in Experiment Nos. 1-13, 1-14, and 1-15 are melted and scattered filters.

排ガス処理材の酸性ガス固定化能力を検討した。表2に示す排ガス処理材を使用い、小型焼却炉の排ガス通路の温度が650〜750℃となる位置に20kgのペレット状のガスフィルターを配設し、実施例1と同様の方法でガスフィルターに塩素成分とイオウ成分を吸蔵させた。排ガス処理後のガスフィルターを回収し、1,300℃で30分熱処理した。1,300℃での熱処理前と熱処理後の塩素及びイオウの含有量の合計を酸性ガス含有量とし、熱処理前後の酸性ガス含有量の比を酸性ガス固定化率とした。結果を表2に示した。比較例として水酸化カルシウムのみを用いた場合や、ハイドロソーダライトを用いた場合の結果も表2に併記した。   The ability of the exhaust gas treatment material to fix acid gas was examined. Using the exhaust gas treatment material shown in Table 2, a 20 kg pellet gas filter is disposed at a position where the temperature of the exhaust gas passage of the small incinerator is 650 to 750 ° C., and the gas filter is processed in the same manner as in Example 1. Occluded the chlorine and sulfur components. The gas filter after exhaust gas treatment was collected and heat treated at 1,300 ° C. for 30 minutes. The total content of chlorine and sulfur before and after heat treatment at 1,300 ° C. was defined as the acid gas content, and the ratio of the acid gas content before and after the heat treatment was defined as the acid gas immobilization rate. The results are shown in Table 2. Table 2 also shows the results when only calcium hydroxide was used as a comparative example and when hydrosodalite was used.

<測定方法>
ガスフィルターの塩素量及びイオウ量:JIS R 5202に準じて定量。
塩素固定化率:排ガス処理後のガスフィルターを回収し、1,300℃で30分熱処理し、1,300℃熱処理前後の塩素量及びイオウ量をもとに酸性ガス含有量を求め、下記の式で酸性ガス固定化率を求めた。
<Measurement method>
Chlorine content and sulfur content of gas filter: Quantified according to JIS R 5202.
Chlorine immobilization rate: The gas filter after exhaust gas treatment is collected, heat treated at 1,300 ° C for 30 minutes, the acid gas content is calculated based on the chlorine amount and sulfur amount before and after 1,300 ° C heat treatment, and the following formula The immobilization rate was determined.

Figure 0004441225
Figure 0004441225

Figure 0004441225
Figure 0004441225

カルシウムアルミノフェライトを含有する排ガス処理材。本発明の排ガス処理材は、塩化水素とSOXの双方の酸性ガスの固定化能力に優れ、排ガス処理材に酸性ガスが固定化された状態の融点が高く、1,300℃程度の高い温度領域まで酸性ガスを安定して固定化できるため、焼却設備の腐食防止、酸性雨の防止、ダイオキシン生成の抑制等に有効であり、都市ゴミ焼却時に発生する酸性ガスの固定化だけでなく、塩素やイオウを含有する廃棄物である下水汚泥等の汚泥、生コンスラッジやパルプスラッジ等のスラッジを焼却する際に発生する酸性ガスの固定化等にも広範に利用可能である。
An exhaust gas treatment material containing calcium aluminoferrite. The exhaust gas treatment material of the present invention is excellent in the ability to immobilize both hydrogen chloride and SO X acid gas, has a high melting point in the state where the acid gas is immobilized on the exhaust gas treatment material, and has a high temperature range of about 1,300 ° C. Since acid gas can be stably fixed, it is effective for preventing corrosion of incineration equipment, preventing acid rain, suppressing dioxin formation, etc. In addition to fixing of acid gas generated during municipal waste incineration, chlorine and sulfur can also be used. It can also be widely used for fixing sludge such as sewage sludge, which is a waste containing sewage, and acid gas generated when incinerating sludge such as raw consludge and pulp sludge.

Claims (5)

4CaO・Al2O3・Fe2O3にSiO25%添加し溶融後に急冷して得た非晶質のカルシウムアルミノフェライトを含有する排ガス処理材。 An exhaust gas treatment material containing amorphous calcium aluminoferrite obtained by adding 5% SiO 2 to 4CaO · Al 2 O 3 · Fe 2 O 3 and quenching after melting. 水酸化カルシウム、酸化カルシウム、炭酸カルシウムから選ばれる1種又は2種以上を含有する、請求項1記載の排ガス処理材。 The exhaust gas treatment material according to claim 1, comprising one or more selected from calcium hydroxide, calcium oxide, and calcium carbonate. 請求項1〜2のうちの1項に記載の排ガス処理材を成形することを特徴とするガスフィルター。 A gas filter, wherein the exhaust gas treatment material according to claim 1 is molded. 請求項1〜2のうちの1項に記載の排ガス処理材を用いることを特徴とする排ガスの処理方法。 An exhaust gas treatment method using the exhaust gas treatment material according to claim 1. 請求項3記載のガスフィルターを用いることを特徴とする排ガスの処理方法。 An exhaust gas treatment method using the gas filter according to claim 3.
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