WO2012176518A1 - Procédé ainsi qu'agent d'inhibition de salissure et de corrosion - Google Patents

Procédé ainsi qu'agent d'inhibition de salissure et de 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
Authority
WO
WIPO (PCT)
Prior art keywords
substance
dirt
reactant
compound
exhaust gas
Prior art date
Application number
PCT/JP2012/057214
Other languages
English (en)
Japanese (ja)
Inventor
藤田　聡
匡彦 満田
Original Assignee
栗田工業株式会社
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 栗田工業株式会社 filed Critical 栗田工業株式会社
Publication of WO2012176518A1 publication Critical patent/WO2012176518A1/fr

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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.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Gas Separation By Absorption (AREA)
  • Treating Waste Gases (AREA)

Abstract

L'invention a pour objectif de fournir un procédé ainsi qu'un agent permettant d'inhiber la salissure et la corrosion dues à des substances salissantes contenues dans des gaz d'échappement. Le procédé d'inhibition de salissure et de corrosion comporte une étape au cours de laquelle un réactif est mis en contact avec un gaz d'échappement qui contient les substances salissantes contenant à leur tour au moins un composé choisi dans un groupe constitué d'un composé chlorure, d'un composé acide sulfurique et d'un composé hydrogénosulfate, permettant ainsi de faire réagir le réactif avec les substances salissantes, et de transformer ces dernières en liquide ou en gaz. De préférence, le réactif contient un composé ammonium quaternaire.
PCT/JP2012/057214 2011-06-24 2012-03-21 Procédé ainsi qu'agent d'inhibition de salissure et de corrosion WO2012176518A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011-141148 2011-06-24
JP2011141148A JP2013006156A (ja) 2011-06-24 2011-06-24 汚れ及び腐食の抑制方法及び抑制剤

Publications (1)

Publication Number Publication Date
WO2012176518A1 true WO2012176518A1 (fr) 2012-12-27

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PCT/JP2012/057214 WO2012176518A1 (fr) 2011-06-24 2012-03-21 Procédé ainsi qu'agent d'inhibition de salissure et de corrosion

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JP (1) JP2013006156A (fr)
WO (1) WO2012176518A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5850070B2 (ja) * 2014-02-12 2016-02-03 栗田工業株式会社 燃焼装置の排ガス流路の汚れ防止方法、及び燃焼装置の排ガスに含まれる硫酸水素アンモニウムの除去方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0857246A (ja) * 1994-05-26 1996-03-05 Tama Kagaku Kogyo Kk 酸性排ガスの処理方法
JP2006095424A (ja) * 2004-09-29 2006-04-13 Kurita Water Ind Ltd 煙道処理剤及び煙道処理方法
JP2008253877A (ja) * 2007-03-30 2008-10-23 Mitsui Eng & Shipbuild Co Ltd 排ガス処理装置及び方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0857246A (ja) * 1994-05-26 1996-03-05 Tama Kagaku Kogyo Kk 酸性排ガスの処理方法
JP2006095424A (ja) * 2004-09-29 2006-04-13 Kurita Water Ind Ltd 煙道処理剤及び煙道処理方法
JP2008253877A (ja) * 2007-03-30 2008-10-23 Mitsui Eng & Shipbuild Co Ltd 排ガス処理装置及び方法

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