WO2012176518A1 - Method and agent for inhibiting staining and corrosion - Google Patents

Method and agent for inhibiting staining and corrosion Download PDF

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Publication number
WO2012176518A1
WO2012176518A1 PCT/JP2012/057214 JP2012057214W WO2012176518A1 WO 2012176518 A1 WO2012176518 A1 WO 2012176518A1 JP 2012057214 W JP2012057214 W JP 2012057214W WO 2012176518 A1 WO2012176518 A1 WO 2012176518A1
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substance
dirt
reactant
compound
exhaust gas
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PCT/JP2012/057214
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French (fr)
Japanese (ja)
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藤田　聡
匡彦 満田
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栗田工業株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/68—Halogens or halogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/80—Organic bases or salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/202—Single element halogens
    • B01D2257/2025—Chlorine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds

Definitions

  • the present invention relates to a method and an inhibitor for suppressing dirt and corrosion caused by dirt substances contained in exhaust gas.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method and a preparation capable of suppressing dirt and corrosion due to dirt substances in exhaust gas.
  • the present inventors have found that the soil is fundamentally suppressed by liquefying or vaporizing the soil material, and the present invention has been completed. Specifically, the present invention provides the following.
  • the reactant is reacted with the dirt substance by contacting the reactant with an exhaust gas containing a dirt substance containing one or more selected from the group consisting of a chlorine compound, a sulfate compound, and a hydrogen sulfate compound,
  • a method for suppressing dirt and corrosion comprising a step of liquefying or vaporizing a dirt substance.
  • solid adhesion to the exhaust gas flow path is suppressed by liquefying or vaporizing the dirt substance.
  • dirt and corrosion due to dirt substances in the exhaust gas can be suppressed.
  • FIG. 1 is a schematic diagram of a system for performing a method according to an embodiment of the present invention.
  • the method according to the embodiment of the present invention includes a step of bringing a reactant into contact with an exhaust gas containing a dirt substance to cause the reactant to react with the dirt substance to be liquefied or vaporized.
  • a dirt substance to change the soil material to another material having a low melting point or a low deliquescence temperature and / or a low boiling point, a low sublimation temperature, or a low decomposition temperature by the above reaction.
  • the fouling substance contains one or more selected from the group consisting of chlorine compounds, sulfuric acid compounds, and hydrogen sulfate compounds, and is easily solidified and adhered to the exhaust gas flow path at, for example, 100 to 350 ° C.
  • Examples of chlorine compounds include hydrogen chloride and ammonium chloride.
  • Examples of the sulfuric acid compound include sulfuric acid and ammonium sulfate.
  • Examples of the hydrogen sulfate compound include ammonium hydrogen sulfate.
  • the above-mentioned another substance may be appropriately set so as not to be solidified according to the pressure, temperature, composition, etc. of the atmosphere of the system through which the exhaust gas flows.
  • the another substance preferably includes a substance having a melting point lower than the lowest temperature of the atmosphere of the system through which the exhaust gas flows.
  • the system through which the exhaust gas flows refers to a flow path from when the fuel is burned to generate exhaust gas until the exhaust gas is released to the outside air.
  • the minimum temperature refers to the lowest temperature among exhaust gas temperatures at a plurality of locations in the system.
  • the above-mentioned another substance preferably includes a substance having a melting point of 200 ° C. or lower, more preferably 180 ° C. or lower, in that it is difficult to solidify under various conditions.
  • the other substance includes a substance having a boiling point of 350 ° C. or lower or decomposing at 350 ° C. or lower.
  • the temperature is more preferably 250 ° C. or lower.
  • the reactant used in the present invention is not particularly limited as long as the contaminant can be liquefied or vaporized.
  • a quaternary ammonium compound is preferable, for example, represented by the following chemical formula.
  • R1, R2 and R3 are each independently an alkyl group having 1 or more carbon atoms which may have a hydroxyl group, and n is an integer of 1 or more.
  • the quaternary ammonium compound is not particularly limited, but hydroxymethyltrimethylammonium hydroxide, hydroxymethyltriethylammonium hydroxide, hydroxyethyltrimethylammonium hydroxide, (2-hydroxyethyl) triethylammonium hydroxide, (3-hydroxypropyl) One or more of trimethylammonium hydroxide and the like may be used. Of these, (2-hydroxyethyl) triethylammonium hydroxide (hereinafter also referred to as choline hydroxide) is preferable. Choline hydroxide alone or in combination with an alkaline substance such as choline hydroxide and other organic amines. Also good.
  • the reactant may be introduced by itself or in the form of a 99% or less (preferably 50% or less) solution (water or other solvent).
  • the amount of reactant introduced is preferably adjusted based on the amount of fouling material. Specifically, the amount of reactant introduced is 0.1% relative to the minimum amount of SO3, HCl and NH3. The above amount (molar ratio) is preferable, and the total amount is preferably 5.0 or lower (molar ratio). If the introduced amount of the reactant is too small, the remaining of the dirt substance cannot be prevented sufficiently, and even if it is too large, the effect of suppressing the stain is saturated and the reactant is wasted.
  • the location where contamination and corrosion should be suppressed is not particularly limited, but may be, for example, a location where the exhaust gas temperature is 350 ° C. or lower, specifically 100 to 350 ° C.
  • the solution may be introduced as it is or sprayed at a high pressure (for example, 0.1 to 5.0 MPa) (droplet diameter may be 2 to 3000 ⁇ m) or vaporized and introduced together with the carrier gas.
  • a high pressure for example, 0.1 to 5.0 MPa
  • droplet diameter may be 2 to 3000 ⁇ m
  • the pipe may be formed of a material that is not easily corroded, such as stainless steel, and in order to further suppress corrosion due to high temperature exhaust gas, the pipe has a double pipe structure, A refrigerant (for example, air) may be passed between the tubes.
  • a refrigerant for example, air
  • the amount of reactant introduced may be constant or variable. In the case where the amount of the fouling substance varies depending on the input amount and properties of the fuel, it is preferable to optimize the introduction amount of the reactant.
  • the introduction method may be continuous or intermittent. When the reactant is introduced intermittently, the introduction time may be several minutes to several hours / time, and the frequency may be one time / day or more.
  • the present invention also includes a stain and corrosion inhibitor caused by a soil material containing at least one selected from the group consisting of chlorine compounds, sulfuric acid compounds, and hydrogen sulfate compounds.
  • the inhibitor has a chemical structure that reacts with the soil material to change it to another material having a lower melting point or lower deliquescence temperature and / or lower boiling point or lower sublimation temperature and lower decomposition temperature than the soil material.
  • a quaternary ammonium compound may be included. Since other description is the same as the description regarding the method, it is omitted.
  • a quartz glass tube is installed inside a tubular electric furnace.
  • the quartz glass tube has, at the top, a hole for inserting a cork and a hole for introducing a reactant.
  • a cork member having an air suction port and a port through which a rod for fixing the test piece is inserted is inserted into the hole.
  • a plate in which 0.3 g of ammonium sulfate, ammonium hydrogen sulfate, or ammonium chloride was uniformly spread on a 10 mm ⁇ 10 mm ⁇ 1 mm mild steel plate was used.
  • Air with a moisture pressure of 0.1 atm was passed through a quartz glass tube by a suction pump, and the temperature in the electric furnace was raised to each temperature shown in Table 1.
  • a 48% choline hydroxide aqueous solution (reactant) While being vaporized, it was introduced into a quartz glass tube.
  • the test piece was taken out, and the state of each substance on the test piece was observed (gas: disappearance, liquid: dripping, solid: powder or the same as before heating).
  • 0.5% aqueous solution (0.1g / 20mL water) of each substance on a test piece was prepared, and pH at 25 degreeC was measured.
  • the test piece was subjected to derusting treatment, and the corrosion rate was determined from the mass difference before and after the test piece. The results are shown in Table 1.
  • the substances on the test piece were not solidified at each temperature (particularly 100 to 300 ° C.) as compared to the comparative examples where the reactants were not added. It changed to (choline hydroxide salt), and corrosion of the test piece was suppressed.
  • Example 2 Heating was performed under the same conditions as in the examples except that the material spread on the test piece was ammonium sulfate and the material to be introduced was changed to choline sulfate hydroxide or oil-soluble organic magnesium salt. The results are shown in Table 2.

Abstract

The purpose of the present invention is to provide a method and a preparation, both of which can inhibit staining and corrosion caused by a staining substance in an exhaust gas. A method for inhibiting staining and corrosion according to the present invention comprises a step of bringing an exhaust gas that contains a staining substance comprising at least one compound selected from the group consisting of a chlorine compound, a sulfuric acid compound and a hydrogen sulfate compound into contact with a reactant to cause the reaction between the staining substance and the reactant, thereby liquefying or gasifying the staining substance. Preferably, the reactant contains a quaternary ammonium compound.

Description

汚れ及び腐食の抑制方法及び抑制剤Stain and corrosion control method and inhibitor
　本発明は、排ガスに含まれる汚れ物質による汚れ及び腐食の抑制方法及び抑制剤に関する。 The present invention relates to a method and an inhibitor for suppressing dirt and corrosion caused by dirt substances contained in exhaust gas.
　燃焼設備では、燃料や廃棄物を焼却すると、ＳＯｘ、ＨＣｌ、ＮＨ３等の物質が発生し、これらを含む排ガスが排出される。また、ＮＯｘ処理設備では、排ガスにＮＨ３が注入される場合がある。このような排ガスは、温度が低下していく過程で、排ガス中の汚れ物質（例えば、硫酸アンモニウム、硫酸水素アンモニウム、塩化アンモニウム、ＳＯ３化合物）が煙道内で析出し、これにより煙道の閉塞、腐食、電気集塵機の通電不良等の不具合を生じさせる場合がある。 In combustion equipment, when fuel and waste are incinerated, substances such as SOx, HCl, NH3, etc. are generated, and exhaust gas containing them is discharged. In the NOx treatment facility, NH3 may be injected into the exhaust gas. In such exhaust gas, in the process of decreasing temperature, dirt substances (for example, ammonium sulfate, ammonium hydrogen sulfate, ammonium chloride, SO3 compound) in the exhaust gas are deposited in the flue, thereby blocking or corroding the flue. In some cases, problems such as poor energization of the electrostatic precipitator may occur.
　従来、ＳＯ３化合物の生成を抑制する技術として、排ガスにＭｇ化合物を導入することで、ＳＯ３化合物の生成触媒であるＶ２Ｏ５等の重金属化合物を不活性化させること、Ｆｅ化合物を燃料に含めることで、未燃炭素の燃焼を促進し、排ガスを低酸素状態にすることが提案されている（特許文献１及び２参照）。また、硫酸塩や塩化物塩の生成を抑制する技術として、燃焼室内にＣａ化合物やＭｇ化合物を導入し、排ガスを脱硫、脱塩すること、湿式脱硫塔にＮａ塩を導入し、中和させることが提案されている。 Conventionally, as a technique for suppressing the generation of SO3 compound, by introducing a Mg compound into the exhaust gas, inactivating a heavy metal compound such as V2O5 that is a catalyst for generating the SO3 compound, and including an Fe compound in the fuel, It has been proposed to promote the combustion of unburned carbon and to reduce the exhaust gas to a low oxygen state (see Patent Documents 1 and 2). In addition, as a technique for suppressing the formation of sulfate and chloride salts, Ca and Mg compounds are introduced into the combustion chamber, and exhaust gas is desulfurized and desalted, and Na salt is introduced into the wet desulfurization tower and neutralized. It has been proposed.
特開昭６２－１６７３９１号公報JP 62-167391 A 特開昭６２－１６７３９３号公報JP 62-167393 A
　しかし、前述の方法は、いずれも汚れ物質の生成を予防するものであるが、理論的な観点から、生成を完全に抑制することはできない。 However, all of the above-mentioned methods prevent the generation of dirt substances, but the generation cannot be completely suppressed from a theoretical point of view.
　本発明は、以上の実情に鑑みてなされたものであり、排ガス中の汚れ物質による汚れ及び腐食を抑制することができる方法及び製剤を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method and a preparation capable of suppressing dirt and corrosion due to dirt substances in exhaust gas.
　本発明者らは、汚れ物質を液化又は気化させることで、汚れを根本的に抑制することを見出し、本発明を完成するに至った。具体的に、本発明は以下のものを提供する。 The present inventors have found that the soil is fundamentally suppressed by liquefying or vaporizing the soil material, and the present invention has been completed. Specifically, the present invention provides the following.
　（１）　塩素化合物、硫酸化合物、及び硫酸水素化合物からなる群より選ばれる１種以上を含む汚れ物質を含む排ガスに反応体を接触させることで、前記反応体を前記汚れ物質と反応させ、前記汚れ物質を液化又は気化させる工程を有する汚れ及び腐食の抑制方法。 (1) The reactant is reacted with the dirt substance by contacting the reactant with an exhaust gas containing a dirt substance containing one or more selected from the group consisting of a chlorine compound, a sulfate compound, and a hydrogen sulfate compound, A method for suppressing dirt and corrosion comprising a step of liquefying or vaporizing a dirt substance.
　（２）　前記反応体は、第４級アンモニウム化合物を含む（１）記載の方法。 (2) The method according to (1), wherein the reactant includes a quaternary ammonium compound.
　（３）　塩素化合物、硫酸化合物、及び硫酸水素化合物からなる群より選ばれる１種以上を含む汚れ物質による汚れ及び腐食の抑制剤であって、
　前記汚れ物質と反応して、前記汚れ物質を液化又は気化させる抑制剤。 (3) An inhibitor of dirt and corrosion caused by a dirt substance containing at least one selected from the group consisting of chlorine compounds, sulfuric acid compounds, and hydrogen sulfate compounds,
An inhibitor that reacts with the dirt substance to liquefy or vaporize the dirt substance.
　（４）　第４級アンモニウム化合物を含む（３）記載の抑制剤。 (4) The inhibitor according to (3), comprising a quaternary ammonium compound.
　本発明によれば、汚れ物質を液化又は気化させることで、排ガス流路への固体付着が抑制される。これにより、排ガス中の汚れ物質による汚れ及び腐食を抑制することができる。 According to the present invention, solid adhesion to the exhaust gas flow path is suppressed by liquefying or vaporizing the dirt substance. Thereby, dirt and corrosion due to dirt substances in the exhaust gas can be suppressed.
本発明の一実施例に係る方法を行う系の概略図である。1 is a schematic diagram of a system for performing a method according to an embodiment of the present invention.
　以下、本発明の実施形態について説明するが、それらに本発明が限定されるものではない。 Hereinafter, embodiments of the present invention will be described, but the present invention is not limited thereto.
　本発明の実施形態に係る方法は、汚れ物質を含む排ガスに反応体を接触することで、この反応体を汚れ物質と反応させ、液化又は気化させる工程を有する。具体的には、上記反応により、汚れ物質より低融点もしくは低潮解温度、かつ／又は、低沸点もしくは低昇華温度、低分解温度の別物質へと変化させることが好ましい。汚れ物質は、塩素化合物、硫酸化合物、及び硫酸水素化合物からなる群より選ばれる１種以上を含み、例えば１００～３５０℃の排ガスの流路に固化して付着しやすい。このような汚れ物質を上記の別物質へと化学的に変化させると、かかる物質は液化、気化又は分解しやすいため、汚れの付着及び腐食を抑制することができる。 The method according to the embodiment of the present invention includes a step of bringing a reactant into contact with an exhaust gas containing a dirt substance to cause the reactant to react with the dirt substance to be liquefied or vaporized. Specifically, it is preferable to change the soil material to another material having a low melting point or a low deliquescence temperature and / or a low boiling point, a low sublimation temperature, or a low decomposition temperature by the above reaction. The fouling substance contains one or more selected from the group consisting of chlorine compounds, sulfuric acid compounds, and hydrogen sulfate compounds, and is easily solidified and adhered to the exhaust gas flow path at, for example, 100 to 350 ° C. When such a dirt substance is chemically changed to the above-mentioned another substance, such a substance is liable to be liquefied, vaporized, or decomposed, so that adhesion and corrosion of the dirt can be suppressed.
　塩素化合物としては、塩化水素、塩化アンモニウムが挙げられる。硫酸化合物としては、硫酸、硫酸アンモニウムが挙げられる。硫酸水素化合物としては、硫酸水素アンモニウムが挙げられる。 Examples of chlorine compounds include hydrogen chloride and ammonium chloride. Examples of the sulfuric acid compound include sulfuric acid and ammonium sulfate. Examples of the hydrogen sulfate compound include ammonium hydrogen sulfate.
　上記の別物質は、排ガスが流通する系の雰囲気の圧力、温度、組成等に応じ、固化しにくいよう適宜設定されてよい。具体的に、上記の別物質は、排ガスが流通する系の雰囲気の最低温度より低い融点を有する物質を含むことが好ましい。これにより、排ガスが流通する系において、上記の別物質は常に固化しにくい。なお、排ガスが流通する系とは、燃料が燃焼されて排ガスが生成されてから、排ガスが外気へと放出されるまでの流路を指す。最低温度は、系内の複数個所における排ガスの温度のうち最も低い温度を指す。 The above-mentioned another substance may be appropriately set so as not to be solidified according to the pressure, temperature, composition, etc. of the atmosphere of the system through which the exhaust gas flows. Specifically, the another substance preferably includes a substance having a melting point lower than the lowest temperature of the atmosphere of the system through which the exhaust gas flows. As a result, in the system in which the exhaust gas is circulated, the other substance is not always solidified. The system through which the exhaust gas flows refers to a flow path from when the fuel is burned to generate exhaust gas until the exhaust gas is released to the outside air. The minimum temperature refers to the lowest temperature among exhaust gas temperatures at a plurality of locations in the system.
　別の側面で、様々な条件において固化しにくい点で、上記の別物質は、２００℃以下の融点を有する物質を含むことが好ましく、より好ましくは１８０℃以下である。 In another aspect, the above-mentioned another substance preferably includes a substance having a melting point of 200 ° C. or lower, more preferably 180 ° C. or lower, in that it is difficult to solidify under various conditions.
　様々な系において気体でありやすい点で、上記の別物質は、３５０℃以下の沸点を有する又は３５０℃以下で分解する物質を含むことも好ましい。上記温度は、より好ましくは２５０℃以下である。これにより、上記の別物質は、様々な条件において気化又は気体物質へと分解しやすいため、汚れ及び腐食を抑制することができる。 In view of the tendency to be a gas in various systems, it is also preferable that the other substance includes a substance having a boiling point of 350 ° C. or lower or decomposing at 350 ° C. or lower. The temperature is more preferably 250 ° C. or lower. Thereby, since said another substance is easily vaporized or decomposed | disassembled into gaseous substance on various conditions, it can suppress dirt and corrosion.
　本発明で用いる反応体は、汚れ物質を液化又は気化できる限りにおいて特に限定されない。具体的には、第４級アンモニウム化合物が好ましく、例えば以下の化学式で示される。
Figure JPOXMLDOC01-appb-C000001
 　（式中、Ｒ１、Ｒ２及びＲ３は、独立して、ヒドロキシル基を有していてもよい炭素数１以上のアルキル基であり、ｎは１以上の整数である。） The reactant used in the present invention is not particularly limited as long as the contaminant can be liquefied or vaporized. Specifically, a quaternary ammonium compound is preferable, for example, represented by the following chemical formula.
Figure JPOXMLDOC01-appb-C000001
 (In the formula, R1, R2 and R3 are each independently an alkyl group having 1 or more carbon atoms which may have a hydroxyl group, and n is an integer of 1 or more.)
　第４級アンモニウム化合物は、特に限定されないが、ヒドロキシメチルトリメチルアンモニウムハイドロオキサイド、ヒドロキシメチルトリエチルアンモニウムハイドロオキサイド、ヒドロキシエチルトリメチルアンモニウムハイドロオキサイド、（２－ヒドロキシエチル）トリエチルアンモニウムハイドロオキサイド、（３－ヒドロキシプロピル）トリメチルアンモニウムハイドロオキサイド等の１種又は２種以上であってよい。中でも、（２－ヒドロキシエチル）トリエチルアンモニウムハイドロオキサイド（以下、コリンハイドロオキサイドともいう）が好ましく、コリンハイドロオキサイド単独で用いても、コリンハイドロオキサイドと他の有機アミン等のアルカリ性物質とを併用してもよい。 The quaternary ammonium compound is not particularly limited, but hydroxymethyltrimethylammonium hydroxide, hydroxymethyltriethylammonium hydroxide, hydroxyethyltrimethylammonium hydroxide, (2-hydroxyethyl) triethylammonium hydroxide, (3-hydroxypropyl) One or more of trimethylammonium hydroxide and the like may be used. Of these, (2-hydroxyethyl) triethylammonium hydroxide (hereinafter also referred to as choline hydroxide) is preferable. Choline hydroxide alone or in combination with an alkaline substance such as choline hydroxide and other organic amines. Also good.
　反応体は、それ自体で導入されてもよいが、９９％以下（好ましくは５０％以下）の溶液（水又は他の溶媒）の形態で導入されてもよい。いずれの形態においても、反応体の導入量は、汚れ物質の量に基づき調節することが好ましい、具体的に、反応体の導入量は、ＳＯ３、ＨＣｌ及びＮＨ３の最小量に対し、０．１以上（モル比）の量であることが好ましく、合計量の５．０以下（モル比）の量であることが好ましい。反応体の導入量が過小であると、汚れ物質の残存を十分に防止できず、過大であっても、汚れの抑制効果は飽和し、反応体の浪費につながる。 The reactant may be introduced by itself or in the form of a 99% or less (preferably 50% or less) solution (water or other solvent). In any form, the amount of reactant introduced is preferably adjusted based on the amount of fouling material. Specifically, the amount of reactant introduced is 0.1% relative to the minimum amount of SO3, HCl and NH3. The above amount (molar ratio) is preferable, and the total amount is preferably 5.0 or lower (molar ratio). If the introduced amount of the reactant is too small, the remaining of the dirt substance cannot be prevented sufficiently, and even if it is too large, the effect of suppressing the stain is saturated and the reactant is wasted.
　反応体は、排ガスが流通する系において、汚れ及び腐食を抑制すべき箇所又はその上流において導入することが好ましい。汚れ及び腐食を抑制すべき箇所は、特に限定されないが、例えば排ガス温度が３５０℃以下、具体的には１００～３５０℃の箇所であってよい。 It is preferable to introduce the reactants at a location where contamination and corrosion should be suppressed or upstream thereof in a system in which exhaust gas flows. The location where contamination and corrosion should be suppressed is not particularly limited, but may be, for example, a location where the exhaust gas temperature is 350 ° C. or lower, specifically 100 to 350 ° C.
　反応体は、溶液をそのまま導入又は高圧（例えば０．１～５．０ＭＰａ）で噴霧（液滴径が２～３０００μｍであってよい）してもよく、気化させてキャリアガスとともに導入してもよい。反応体の供給管を系内に配置する場合、その管はステンレス鋼等の腐食されにくい素材で形成してよく、高温の排ガスによる腐食をより抑制する観点で、管を二重管構造にし、管同士の間に冷媒（例えば空気）を通してもよい。 As the reactant, the solution may be introduced as it is or sprayed at a high pressure (for example, 0.1 to 5.0 MPa) (droplet diameter may be 2 to 3000 μm) or vaporized and introduced together with the carrier gas. Good. When the reactant supply pipe is arranged in the system, the pipe may be formed of a material that is not easily corroded, such as stainless steel, and in order to further suppress corrosion due to high temperature exhaust gas, the pipe has a double pipe structure, A refrigerant (for example, air) may be passed between the tubes.
　また、反応体の導入量は、一定でも、変動でもよい。燃料の投入量や性状により、汚れ物質の量が変動する場合、反応体の導入量を適正化することがに好ましい。また、導入方法は、連続でも間欠でもよい。反応体の導入を間欠で行う場合、導入時間は数分～数時間／回、頻度は１回／日以上であってよい。 Also, the amount of reactant introduced may be constant or variable. In the case where the amount of the fouling substance varies depending on the input amount and properties of the fuel, it is preferable to optimize the introduction amount of the reactant. The introduction method may be continuous or intermittent. When the reactant is introduced intermittently, the introduction time may be several minutes to several hours / time, and the frequency may be one time / day or more.
　本発明は、塩素化合物、硫酸化合物、及び硫酸水素化合物からなる群より選ばれる１種以上を含む汚れ物質による汚れ及び腐食の抑制剤も包含する。抑制剤は、汚れ物質と反応して、汚れ物質より低融点もしくは低潮解温度、かつ／又は、低沸点もしくは低昇華温度、低分解温度の別物質へと変化させる化学的構造を有する。具体的には、第４級アンモニウム化合物を含んでよい。他の説明は、方法に関する説明と同様であるため、省略する。 The present invention also includes a stain and corrosion inhibitor caused by a soil material containing at least one selected from the group consisting of chlorine compounds, sulfuric acid compounds, and hydrogen sulfate compounds. The inhibitor has a chemical structure that reacts with the soil material to change it to another material having a lower melting point or lower deliquescence temperature and / or lower boiling point or lower sublimation temperature and lower decomposition temperature than the soil material. Specifically, a quaternary ammonium compound may be included. Since other description is the same as the description regarding the method, it is omitted.
　＜実施例１＞
　図１に示す装置において、管状の電気炉の内部に、石英ガラス管を設置した。石英ガラス管は、上部に、コルクを挿入する穴と、反応体を導入する穴とを有する。その穴に、空気吸入口、及び試験片を固定する棒を挿通する口を有するコルク部材を挿入した。試験片としては、１０ｍｍ×１０ｍｍ×１ｍｍの軟鋼製の板の上に、硫酸アンモニウム、硫酸水素アンモニウム、又は塩化アンモニウム０．３ｇを均一に敷き詰めたものを用いた。 <Example 1>
In the apparatus shown in FIG. 1, a quartz glass tube is installed inside a tubular electric furnace. The quartz glass tube has, at the top, a hole for inserting a cork and a hole for introducing a reactant. A cork member having an air suction port and a port through which a rod for fixing the test piece is inserted is inserted into the hole. As the test piece, a plate in which 0.3 g of ammonium sulfate, ammonium hydrogen sulfate, or ammonium chloride was uniformly spread on a 10 mm × 10 mm × 1 mm mild steel plate was used.
　吸引ポンプにより水分圧０．１ａｔｍの空気を石英ガラス管へと通し、電気炉内を表１に示す各温度へと昇温し、温度が安定した後、コリンハイドロオキサイド４８％水溶液（反応体）を気化した状態で、石英ガラス管へと導入した。１８時間経過した後、試験片を取り出し、試験片上の各物質の状態を観察（気体：消失、液体：液だれ、固体：粉末又は加熱前と同じ）した。また、試験片を室温まで冷やした後、試験片上の各物質の０．５％水溶液（０．１ｇ／２０ｍＬ水）を調製し、２５℃でのｐＨを測定した。更に、試験片に脱錆処理を施し、その前後での質量差から腐食速度を求めた。この結果を表１に示す。 Air with a moisture pressure of 0.1 atm was passed through a quartz glass tube by a suction pump, and the temperature in the electric furnace was raised to each temperature shown in Table 1. After the temperature was stabilized, a 48% choline hydroxide aqueous solution (reactant) While being vaporized, it was introduced into a quartz glass tube. After 18 hours, the test piece was taken out, and the state of each substance on the test piece was observed (gas: disappearance, liquid: dripping, solid: powder or the same as before heating). Moreover, after cooling a test piece to room temperature, 0.5% aqueous solution (0.1g / 20mL water) of each substance on a test piece was prepared, and pH at 25 degreeC was measured. Furthermore, the test piece was subjected to derusting treatment, and the corrosion rate was determined from the mass difference before and after the test piece. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表１に示されるように、反応体を添加した実施例では、反応体を添加しなかった比較例に比べ、各温度（特に、１００～３００℃）において、試験片上の各物質が固化しない物質（コリンハイドロオキサイド塩）へと変化し、また試験片の腐食が抑制されていた。 As shown in Table 1, in the examples where the reactants were added, the substances on the test piece were not solidified at each temperature (particularly 100 to 300 ° C.) as compared to the comparative examples where the reactants were not added. It changed to (choline hydroxide salt), and corrosion of the test piece was suppressed.
　＜実施例２＞
　試験片の上に敷き詰める物質を、硫酸アンモニウムとし、導入する物質を硫酸コリンハイドロオキサイド又は油溶性有機マグネシウム塩へと変更した点を除き、実施例と同様の条件で、加熱を行った。その結果を表２に示す。 <Example 2>
Heating was performed under the same conditions as in the examples except that the material spread on the test piece was ammonium sulfate and the material to be introduced was changed to choline sulfate hydroxide or oil-soluble organic magnesium salt. The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表２に示されるように、コリンハイドロオキサイドを添加した実施例では、添加しない場合に比べて、各温度（特に、１００～３００℃）において、試験片上の各物質が固化しない物質（コリンハイドロオキサイド塩）へと変化し、また試験片の腐食が抑制されていた。しかし、油溶性有機マグネシウム塩を添加した場合、反応生成物が硫酸マグネシウム（固形物）として試験片に残存した。これは、実際の系において、汚れ成分として系内に汚れが残るということを意味する。また、無処理に比べ、腐食速度は低下するが、コリンハイドロオキサイド程の腐食抑制効果は見られなかった。 As shown in Table 2, in the examples in which choline hydroxide was added, the substances on the test piece were not solidified (choline hydroxide) at each temperature (particularly 100 to 300 ° C.) as compared to the case where no choline hydroxide was added. Salt) and the corrosion of the test piece was suppressed. However, when an oil-soluble organic magnesium salt was added, the reaction product remained on the test piece as magnesium sulfate (solid). This means that in an actual system, dirt remains as a dirt component in the system. In addition, although the corrosion rate was lower than that of no treatment, the corrosion inhibitory effect was not as good as that of choline hydroxide.

Claims (4)

  1. 　塩素化合物、硫酸化合物、及び硫酸水素化合物からなる群より選ばれる１種以上を含む汚れ物質を含む排ガスに反応体を接触させることで、前記反応体を前記汚れ物質と反応させ、前記汚れ物質を液化又は気化させる工程を有する汚れ及び腐食の抑制方法。 The reactant is reacted with the dirt substance by bringing the reactant into contact with an exhaust gas containing a dirt substance containing at least one selected from the group consisting of a chlorine compound, a sulfuric acid compound, and a hydrogen sulfate compound, A method for suppressing dirt and corrosion comprising a step of liquefying or vaporizing.
  2. 　前記反応体は、第４級アンモニウム化合物を含む請求項１記載の方法。 The method of claim 1, wherein the reactant comprises a quaternary ammonium compound.
  3. 　塩素化合物、硫酸化合物、及び硫酸水素化合物からなる群より選ばれる１種以上を含む汚れ物質による汚れ及び腐食の抑制剤であって、
    　前記汚れ物質と反応して、前記汚れ物質を液化又は気化させる抑制剤。     An inhibitor of dirt and corrosion caused by a dirt substance containing at least one selected from the group consisting of chlorine compounds, sulfuric acid compounds, and hydrogen sulfate compounds,
    An inhibitor that reacts with the dirt substance to liquefy or vaporize the dirt substance.
  4. 　第４級アンモニウム化合物を含む請求項３記載の抑制剤。 The inhibitor according to claim 3, comprising a quaternary ammonium compound.
PCT/JP2012/057214 2011-06-24 2012-03-21 Method and agent for inhibiting staining and corrosion WO2012176518A1 (en)

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JPH0857246A (en) * 1994-05-26 1996-03-05 Tama Kagaku Kogyo Kk Treatment of acidic exhaust gas
JP2006095424A (en) * 2004-09-29 2006-04-13 Kurita Water Ind Ltd Flue treating agent and flue treating method
JP2008253877A (en) * 2007-03-30 2008-10-23 Mitsui Eng & Shipbuild Co Ltd Exhaust gas-treating device and method

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0857246A (en) * 1994-05-26 1996-03-05 Tama Kagaku Kogyo Kk Treatment of acidic exhaust gas
JP2006095424A (en) * 2004-09-29 2006-04-13 Kurita Water Ind Ltd Flue treating agent and flue treating method
JP2008253877A (en) * 2007-03-30 2008-10-23 Mitsui Eng & Shipbuild Co Ltd Exhaust gas-treating device and method

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