JP6223791B2 - Method for removing lead from cement firing equipment - Google Patents
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- JP6223791B2 JP6223791B2 JP2013237577A JP2013237577A JP6223791B2 JP 6223791 B2 JP6223791 B2 JP 6223791B2 JP 2013237577 A JP2013237577 A JP 2013237577A JP 2013237577 A JP2013237577 A JP 2013237577A JP 6223791 B2 JP6223791 B2 JP 6223791B2
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- 239000004568 cement Substances 0.000 title claims description 64
- 238000000034 method Methods 0.000 title claims description 25
- 238000010304 firing Methods 0.000 title claims description 19
- 239000000292 calcium oxide Substances 0.000 claims description 19
- 239000000567 combustion gas Substances 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 239000000446 fuel Substances 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 230000003009 desulfurizing effect Effects 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- 239000000284 extract Substances 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 31
- 235000012255 calcium oxide Nutrition 0.000 description 16
- 239000000460 chlorine Substances 0.000 description 13
- 229910052801 chlorine Inorganic materials 0.000 description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 12
- 239000002699 waste material Substances 0.000 description 8
- 239000000428 dust Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229940056932 lead sulfide Drugs 0.000 description 1
- 229910052981 lead sulfide Inorganic materials 0.000 description 1
- XCAUINMIESBTBL-UHFFFAOYSA-N lead(ii) sulfide Chemical compound [Pb]=S XCAUINMIESBTBL-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- Treating Waste Gases (AREA)
Description
本発明は、鉛含有廃棄物及び硫黄含有廃棄物の有効利用を図りながら、セメントの品質に影響を与えることなくセメント焼成装置から鉛を除去する方法に関する。 The present invention relates to a method of removing lead from a cement firing apparatus without affecting the quality of cement while effectively utilizing lead-containing waste and sulfur-containing waste.
近年のセメント製造工程におけるリサイクル資源の活用量の増加に伴い、廃棄物由来の鉛が許容量を超えてセメント製品中に含まれる可能性がある。 With the increase in the amount of recycled resources used in the cement manufacturing process in recent years, there is a possibility that lead derived from waste exceeds the allowable amount and is contained in cement products.
そこで、例えば、特許文献１等には、セメントキルンで揮発した鉛をセメントキルンに付設されている塩素バイパスシステムで回収したダストを介してセメント焼成装置の系外に排出することで、セメント焼成装置から鉛を除去する方法が記載されている。ここで、セメントキルンでの鉛の揮発率を高めることで鉛の除去率が向上する。 Therefore, for example, in Patent Document 1 and the like, a cement firing device is provided by discharging lead volatilized in a cement kiln out of the cement firing device via dust collected by a chlorine bypass system attached to the cement kiln. A method is described for removing lead from water. Here, the lead removal rate is improved by increasing the volatilization rate of lead in the cement kiln.
セメントキルンでの鉛の揮発を促進する技術としては、塩化揮発法と還元揮発法が知られている。塩化揮発法は、鉛を塩化すると揮発し易くなる性質を利用したものであり、原料等に含まれる鉛を塩化物（ＰｂＣｌ2）にして揮発させる。一方、還元揮発法は、炉内を還元雰囲気に調整し、酸化鉛（ＰｂＯ）を還元して鉛（Ｐｂ）を揮発させる。 As a technique for promoting the volatilization of lead in a cement kiln, a chloride volatilization method and a reduction volatilization method are known. The chlorination volatilization method utilizes the property of being easily volatilized when chlorinating lead, and volatilizes lead contained in the raw material as chloride (PbCl 2 ). On the other hand, the reduction volatilization method adjusts the inside of the furnace to a reducing atmosphere, reduces lead oxide (PbO), and volatilizes lead (Pb).
しかし、塩化揮発法の場合には、塩素がセメント製造工程やセメントの品質に悪影響を及ぼすため、セメント焼成に適用するのは技術的に困難な状況にあった。一方、還元揮発法を適用すると、セメントの色が黄色を呈することとなるため、セメントの品質の面で問題があった。 However, in the case of the chlorination volatilization method, chlorine has an adverse effect on the cement manufacturing process and the cement quality, so that it has been technically difficult to apply to cement firing. On the other hand, when the reduction volatilization method is applied, since the color of the cement exhibits a yellow color, there is a problem in terms of cement quality.
そこで、本発明は、上記従来の技術における問題点に鑑みてなされたものであって、鉛含有廃棄物等の有効利用を図りながら、セメントの品質に影響を与えることなくセメント焼成装置から効率よく鉛を除去することを目的とする。 Therefore, the present invention has been made in view of the problems in the above-described conventional technology, and efficiently uses the cement firing apparatus without affecting the cement quality while effectively utilizing the lead-containing waste and the like. The purpose is to remove lead.
上記目的を達成するため、本発明は、セメントキルンの窯尻から最下段サイクロンに至るまでのセメントキルン排ガス流路より燃焼ガスの一部を抽気し、抽気された燃焼ガスに含まれる鉛を回収するセメント焼成装置からの鉛除去方法において、該セメント焼成装置で生成されるセメントクリンカのＳＯ3／ＣａＯ質量比を０．０１４以下に制御することを特徴とする。 In order to achieve the above object, the present invention extracts a part of the combustion gas from the cement kiln exhaust gas flow path from the bottom of the kiln of the cement kiln to the lowermost cyclone, and recovers lead contained in the extracted combustion gas. In the method for removing lead from the cement firing apparatus, the SO 3 / CaO mass ratio of the cement clinker produced by the cement firing apparatus is controlled to 0.014 or less.
本発明によれば、セメントクリンカのＳＯ3／ＣａＯ質量比を０．０１４以下に制御することで、セメントキルンでの鉛の揮発率を高め、抽気された燃焼ガスに含まれる鉛の量を増加させることができるため、鉛含有廃棄物及び硫黄含有廃棄物の有効利用を図りながら、セメントの品質に影響を与えることなくセメント焼成装置から鉛を効率よく除去することができる。 According to the present invention, by controlling the SO 3 / CaO mass ratio of cement clinker to 0.014 or less, the volatilization rate of lead in the cement kiln is increased and the amount of lead contained in the extracted combustion gas is increased. Therefore, it is possible to efficiently remove lead from the cement baking apparatus without affecting the quality of the cement while effectively using the lead-containing waste and the sulfur-containing waste.
上記セメント焼成装置からの鉛除去方法において、セメント焼成装置に供給される原燃料の硫黄分含有率を調整することにより、前記ＳＯ3／ＣａＯ質量比を制御することができる。原燃料の硫黄分含有率は、その種類と使用量を変更することなどで調整することができる。 In the method for removing lead from the cement baking apparatus, the SO 3 / CaO mass ratio can be controlled by adjusting the sulfur content of the raw fuel supplied to the cement baking apparatus. The sulfur content of the raw fuel can be adjusted by changing the type and amount used.
また、前記抽気された燃焼ガスを脱硫することにより、前記ＳＯ3／ＣａＯ質量比を制御することもできる。すなわち、前記燃焼ガスはセメント焼成装置に戻すため、セメント焼成装置内におけるＳＯ3濃縮率が高まる。その際、前記抽気された燃焼ガスを脱硫処理し、ＳＯ3分を工程外に排出することによりこのＳＯ3の濃縮を回避し、ＳＯ3／ＣａＯ質量比を適正に保つことが可能となる。 Further, the SO 3 / CaO mass ratio can be controlled by desulfurizing the extracted combustion gas. That is, since the combustion gas is returned to the cement baking apparatus, the SO 3 concentration rate in the cement baking apparatus is increased. At this time, the extracted combustion gas is desulfurized, and the SO 3 component is discharged out of the process, so that the concentration of SO 3 can be avoided and the SO 3 / CaO mass ratio can be maintained appropriately.
前記燃焼ガスを脱硫するにあたり、前記燃焼ガスに水酸化ナトリウム、炭酸水素ナトリウム、水酸化カルシウム及び水酸化マグネシウム等のＳＯ2と反応する薬剤から選択される１種以上を添加することができる。 In desulfurizing the combustion gas, one or more selected from chemicals that react with SO 2 such as sodium hydroxide, sodium bicarbonate, calcium hydroxide, and magnesium hydroxide can be added to the combustion gas.
以上のように、本発明によれば、鉛含有廃棄物等の有効利用を図りながら、セメントの品質に影響を与えることなくセメント焼成装置から効率よく鉛を除去することができる。 As described above, according to the present invention, lead can be efficiently removed from a cement firing device without affecting the quality of cement while effectively utilizing lead-containing wastes and the like.
図１は、本発明に係るセメント焼成装置からの鉛除去方法において用いる塩素バイパスシステムを示し、この塩素バイパスシステム１は、セメントキルン２の窯尻から最下段サイクロン（不図示）に至るまでのキルン排ガス流路より燃焼ガスの一部Ｇ１をプローブ３で抽気すると同時に、冷却ファン４からの冷風で抽気ガスＧ１をＫＣｌ等の塩素化合物の融点以下（６００℃以下）に冷却し、抽気ガスＧ２をサイクロン５で粗粉Ｄ１を分離した後の抽気ガスＧ３に含まれる、塩素が濃縮した１０μｍ程度以下の微粉Ｄ２をバグフィルタ８で微粉Ｄ４として回収する。この微粉Ｄ４と、冷却器６から回収された微粉Ｄ３とを塩素バイパスダストＤ５として系外に排出して塩素及び鉛等の重金属類を除去する。一方、バグフィルタ８の排ガスＧ４は、排気ファン１０によってセメント焼成装置（セメントキルン２に付設されたプレヒータ等）に戻す。 FIG. 1 shows a chlorine bypass system used in a method for removing lead from a cement firing apparatus according to the present invention. This chlorine bypass system 1 is a kiln extending from the kiln bottom of a cement kiln 2 to a lowermost cyclone (not shown). A part of the combustion gas G1 is extracted by the probe 3 from the exhaust gas flow path, and at the same time, the extraction gas G1 is cooled to below the melting point (600 ° C. or less) of a chlorine compound such as KCl by the cold air from the cooling fan 4. The fine powder D2 of about 10 μm or less concentrated in chlorine contained in the extraction gas G3 after separating the coarse powder D1 with the cyclone 5 is recovered as fine powder D4 by the bag filter 8. The fine powder D4 and the fine powder D3 collected from the cooler 6 are discharged out of the system as chlorine bypass dust D5 to remove heavy metals such as chlorine and lead. On the other hand, the exhaust gas G4 from the bag filter 8 is returned to the cement baking apparatus (such as a preheater attached to the cement kiln 2) by the exhaust fan 10.
塩素バイパスダストＤ５に含まれる鉛を除去するには、塩素バイパスダストＤ５を水に溶解させてスラリー化し、硫化剤等の薬液を添加し、スラリーに含まれる塩化鉛等を硫化して硫化鉛（ＰｂＳ）を生じさせて沈殿させ、浮遊選鉱法等により回収することができる。 In order to remove lead contained in the chlorine bypass dust D5, the chlorine bypass dust D5 is dissolved in water to form a slurry, a chemical solution such as a sulfiding agent is added, and lead chloride contained in the slurry is sulfided to lead sulfide ( PbS) can be generated and precipitated, and recovered by a flotation method or the like.
本発明では、上記セメントキルン２を備えたセメント焼成装置で生成されるセメントクリンカのＳＯ3／ＣａＯ質量比を０．０１４以下、好ましくは０．０１２以下に制御する。 In the present invention, the SO 3 / CaO mass ratio of the cement clinker produced by the cement baking apparatus provided with the cement kiln 2 is controlled to 0.014 or less, preferably 0.012 or less.
図２は、セメントクリンカのＳＯ3／ＣａＯ質量比と鉛除去率の関係を示すグラフである。鉛除去率は、鉛除去率（％）＝［１−セメントクリンカ中のＰｂ含有量（ｋｇ／ｔ−クリンカ）／セメント原燃料中のＰｂ含有量（ｋｇ／ｔ−クリンカ）］×１００により算出した。同グラフより、ＳＯ3／ＣａＯ質量比を０．０１４以下とすることで鉛除去率が５０％以上となり、ＳＯ3／ＣａＯ質量比を０．０１２以下とすることで鉛除去率が６０％以上となることが判る。 FIG. 2 is a graph showing the relationship between the SO 3 / CaO mass ratio of cement clinker and the lead removal rate. Lead removal rate is calculated by lead removal rate (%) = [1-Pb content in cement clinker (kg / t-clinker) / Pb content in raw cement fuel (kg / t-clinker)] × 100 did. From the graph, the lead removal rate is 50% or more when the SO 3 / CaO mass ratio is 0.014 or less, and the lead removal rate is 60% or more when the SO 3 / CaO mass ratio is 0.012 or less. It turns out that it becomes.
ＳＯ3／ＣａＯ質量比を調整するにあたり、原燃料の種類と使用量を変更することが一つの方法である。すなわち、硫黄分含有率の異なる原燃料や硫黄含有廃棄物を複数種類用意し、セメント焼成装置で生成されるセメントクリンカのＳＯ3／ＣａＯ質量比に応じて原燃料の種類を切り換える、又は使用量を調整する。 In adjusting the SO 3 / CaO mass ratio, one method is to change the type and amount of raw fuel used. In other words, multiple types of raw fuel and sulfur-containing wastes with different sulfur contents are prepared, and the type of raw fuel is switched according to the SO 3 / CaO mass ratio of the cement clinker produced by the cement baking equipment, or the amount used Adjust.
また、バグフィルタ８の排ガスＧ４を脱硫することにより、セメントクリンカのＳＯ3／ＣａＯ質量比を制御することもできる。すなわち、排ガスＧ４はセメント焼成装置（セメントキルン２に付設されたプレヒータ等）に戻すため、例えば、排ガスＧ４の脱硫率が低い場合には、セメント焼成装置内におけるＳＯ3濃縮率が高まる。その際、排ガスＧ４を脱硫処理し、ＳＯ3分を工程外に排出することによりこのＳＯ3の濃縮を回避し、ＳＯ3／ＣａＯ質量比を適正に保つことが可能となる。 Further, by desulfurizing the exhaust gas G4 of the bag filter 8, the SO 3 / CaO mass ratio of the cement clinker can be controlled. That is, since the exhaust gas G4 is returned to the cement firing device (such as a preheater attached to the cement kiln 2), for example, when the desulfurization rate of the exhaust gas G4 is low, the SO 3 concentration rate in the cement firing device increases. At that time, the exhaust gas G4 is desulfurized, and the SO 3 component is discharged out of the process, so that the concentration of SO 3 can be avoided and the SO 3 / CaO mass ratio can be maintained appropriately.
排ガスＧ４の脱硫率の調整にあたり、抽気ガスＧ２、Ｇ３及び排ガスＧ４に水酸化ナトリウム、炭酸水素ナトリウム、水酸化カルシウム及び水酸化マグネシウム等のＳＯ2と反応する薬剤から選択される一以上を添加し、それを回収することで対応することができる。また、この脱硫工程に湿式によるシステム、例えば石灰−石膏法か水酸化マグネシウム法等の脱硫設備を設置することもできる。 In adjusting the desulfurization rate of the exhaust gas G4, one or more selected from chemicals that react with SO 2 such as sodium hydroxide, sodium hydrogen carbonate, calcium hydroxide and magnesium hydroxide are added to the extracted gases G2, G3 and the exhaust gas G4. You can respond by collecting it. In addition, a dewatering system such as a lime-gypsum method or a magnesium hydroxide method can be installed in this desulfurization process.
尚、上記実施の形態では、乾式の塩素バイパスシステムを用いたが、湿式塩素バイパスシステムを用いてもよく、湿式の場合には、抽気ガスに含まれる生石灰（ＣａＯ）が水と反応して生じた水酸化カルシウムを脱硫に利用することができる。 In the above embodiment, a dry chlorine bypass system is used. However, a wet chlorine bypass system may be used. In the wet case, quick lime (CaO) contained in the extraction gas reacts with water and is generated. Calcium hydroxide can be used for desulfurization.
また、湿式の場合にも、湿式集塵で得られたスラリーに硫化剤等の薬液を添加し、スラリーに含まれる塩化鉛等を硫化して硫化鉛を生じさせて沈殿させ、浮遊選鉱法等により回収することができる。 Also in the case of wet, a chemical solution such as a sulfiding agent is added to the slurry obtained by wet dust collection, and lead chloride, etc. contained in the slurry is sulfided to produce lead sulfide, which is then precipitated, etc. Can be recovered.
１ 塩素バイパスシステム
２ セメントキルン
３ プローブ
４ 冷却ファン
５ サイクロン
６ 冷却器
８ バグフィルタ
１０ 排気ファン
1 Chlorine bypass system 2 Cement kiln 3 Probe 4 Cooling fan 5 Cyclone 6 Cooler 8 Bag filter 10 Exhaust fan
Claims (4)
該セメント焼成装置で生成されるセメントクリンカのＳＯ3／ＣａＯ質量比を０．０１４以下に制御することを特徴とするセメント焼成装置からの鉛除去方法。 In the lead removal method from the cement firing device that extracts a part of the combustion gas from the cement kiln exhaust gas passage from the bottom of the kiln of the cement kiln to the bottom cyclone, and recovers the lead from the extracted combustion gas,
A method for removing lead from a cement firing device, wherein an SO 3 / CaO mass ratio of a cement clinker produced by the cement firing device is controlled to 0.014 or less.
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| CN114733329B (en) * | 2022-04-02 | 2023-12-08 | 南京西普环保科技有限公司 | Dry desulfurization process and dry desulfurization device for cement clinker |
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| JP2008230942A (en) * | 2007-03-23 | 2008-10-02 | Taiheiyo Cement Corp | Method for treating cement kiln combustion gas extracted dust |
| JP2008231549A (en) * | 2007-03-23 | 2008-10-02 | Taiheiyo Cement Corp | Apparatus and method for treating cement-kiln dust |
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