JPWO2017126652A1 - Cleaning liquid composition for removing sludge and hardened film produced in system containing heavy hydrocarbon or element that gives polarity to molecule, and cleaning method using the same - Google Patents
Cleaning liquid composition for removing sludge and hardened film produced in system containing heavy hydrocarbon or element that gives polarity to molecule, and cleaning method using the same Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/08—Liquid soap, e.g. for dispensers; capsuled
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/06—Hydroxides
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/34—Organic compounds containing sulfur
Abstract
ジメチルスルホキシド、水酸化カリウム、及び水を含む、重質炭化水素又は分子に極性を与える元素を含む系に生成したスラッジ及び硬質化皮膜除去用の洗浄液組成物。A cleaning liquid composition for removing sludge and hardened film formed in a system containing heavy hydrocarbons or elements that impart polarity to molecules, including dimethyl sulfoxide, potassium hydroxide, and water.
Description
本発明は、重質炭化水素又は分子に極性を与える元素を含む系に生成したスラッジ及び硬質化皮膜除去用の洗浄液組成物、ならびにそれを用いた洗浄方法に関する。 The present invention relates to a cleaning liquid composition for removing sludge and hardened film formed in a system containing heavy hydrocarbons or an element that imparts polarity to molecules, and a cleaning method using the same.
炭化水素を反応成分とする化学プロセスやコークス炉ガス（Ｃｏｋｅ Ｏｖｅｎ Ｇａｓ：ＣＯＧ）精製プロセス等に発生する強固な汚れを除去するためには、一般に、洗浄剤を用いた化学洗浄が適用される。 In order to remove strong dirt generated in a chemical process using hydrocarbon as a reaction component, a coke oven gas (Coke Oven Gas: COG) refining process, etc., chemical cleaning using a cleaning agent is generally applied.
しかし、汚れは、プロセス機器を構成する炭素鋼等の材料の腐食物（硫化膜や酸化膜）や原料由来の無機物が混在して安定化していることが多く、従来の洗浄剤では有機分（油分）のみが溶解あるいは乳化除去されるにとどまり、プロセス機器の内部に固着した汚れすべてを除去することはできず、完全に清浄になるとは言い難い。そのため、洗浄剤を用いた化学洗浄後に、さらにウォータージェット洗浄等の物理洗浄が必要になる場合も多く、手間とコストがかかる。 However, dirt is often stabilized by the inclusion of corrosives (sulfide film or oxide film) of materials such as carbon steel and inorganic materials derived from raw materials that make up process equipment. Only the oil component) is dissolved or emulsified and removed, and not all the dirt adhered to the inside of the process equipment can be removed, and it cannot be said that it is completely cleaned. For this reason, it is often necessary to perform physical cleaning such as water jet cleaning after chemical cleaning using a cleaning agent, which requires labor and cost.
固着した被除去物を除去するための洗浄剤としては、例えば、液晶パネルの配向膜を剥離するためのもの（特許文献１）や、注型重合したポリウレタンを除去するためのもの（特許文献２）が開示されている。しかし、炭化水素を反応成分とする化学プロセスやＣＯＧ精製プロセス等のプロセス中に発生した強固な汚れを有効に除去できる洗浄剤及び洗浄方法は知られていない。
Examples of the cleaning agent for removing the fixed object to be removed include those for peeling off the alignment film of the liquid crystal panel (Patent Document 1) and for removing cast polymerized polyurethane (
ＣＯＧ精製プロセスは、高温かつ還元雰囲気で生成されたＣＯＧから、多量に含まれるタールやピッチのような重質油成分、シアン系化合物や硫化水素のような有害物等を順に除去して、ガスをクリーン化するプロセスである。
本発明者らは、ＣＯＧ精製プロセスのいずれの機器においても、スラッジ（固形凝集物）の生成、付着や堆積が多く、また硬質化した皮膜が形成されていることも多いことを見出した。その結果、伝熱効率等の装置効率が低下してしまうため、いかにスラッジや皮膜を効率よく完全に除去するかが課題である。ＣＯＧプロセスは、あらゆる化学プロセスの中で最も汚れる系である。ＣＯＧプロセスを始めとする重質炭化水素油が存在する系において、安定した連続運転を達成するための洗浄技術が求められる。The COG refining process sequentially removes heavy oil components such as tar and pitch, harmful compounds such as cyanide compounds and hydrogen sulfide, etc., in a large amount from COG generated in a high temperature and reducing atmosphere, It is a process to clean up.
The present inventors have found that in any apparatus of the COG refining process, sludge (solid agglomerates) is often generated, adhered and deposited, and a hardened film is often formed. As a result, the efficiency of the apparatus such as the heat transfer efficiency is lowered, so how to efficiently and completely remove the sludge and the film is a problem. The COG process is the most dirty system of any chemical process. In systems where heavy hydrocarbon oils such as the COG process are present, there is a need for a cleaning technique for achieving stable continuous operation.
本発明の目的は、重質炭化水素又は分子に極性を与える元素を含む系に生成したスラッジ及び硬質化皮膜を除去するために有効である新規な洗浄液組成物と、それを用いた洗浄方法を提供することである。 An object of the present invention is to provide a novel cleaning liquid composition effective for removing sludge and hardened film produced in a system containing heavy hydrocarbons or elements that impart polarity to molecules, and a cleaning method using the same. Is to provide.
本発明によれば、以下の重質炭化水素又は分子に極性を与える元素を含む系に生成したスラッジ及び硬質化皮膜除去用の洗浄液組成物等が提供される。
１．ジメチルスルホキシド、水酸化カリウム、及び水を含む、重質炭化水素又は分子に極性を与える元素を含む系に生成したスラッジ及び硬質化皮膜除去用の洗浄液組成物。
２．前記ジメチルスルホキシドの含有量が、前記ジメチルスルホキシド、前記水酸化カリウム、及び前記水の全重量に対して、１０〜８５重量％であり、
前記水酸化カリウムの含有量が、前記ジメチルスルホキシド、前記水酸化カリウム、及び前記水の全重量に対して、５〜３０重量％であり、
前記水の含有量が、前記ジメチルスルホキシド、前記水酸化カリウム、及び前記水の全重量に対して、１０〜６０重量％である、
１に記載の洗浄液組成物。
３．前記ジメチルスルホキシドの含有量が、前記ジメチルスルホキシド、前記水酸化カリウム、及び前記水の全重量に対して、４０〜８５重量％であり、
前記水酸化カリウムの含有量が、前記ジメチルスルホキシド、前記水酸化カリウム、及び前記水の全重量に対して、５〜２５重量％であり、
前記水の含有量が、前記ジメチルスルホキシド、前記水酸化カリウム、及び前記水の全重量に対して、１０〜３５重量％である、
１又は２に記載の洗浄液組成物。
４．前記ジメチルスルホキシドが、使用済みの洗浄液組成物を蒸留することにより回収して再利用したジメチルスルホキシドを含む、１〜３のいずれかに記載の洗浄液組成物。
５．さらにアルコールを含む、１〜４のいずれかに記載の洗浄液組成物。
６．前記アルコールの含有量が、前記ジメチルスルホキシド、前記水酸化カリウム、及び前記水の合計を１００重量部としたときに、１〜１０重量部である、５に記載の洗浄液組成物。
７．さらにＮ−メチルピロリドンを含む、１〜６のいずれかに記載の洗浄剤組成物。
８．前記Ｎ−メチルピロリドンの含有量が、前記ジメチルスルホキシド、前記水酸化カリウム、及び前記水の合計を１００重量部としたときに、５〜３０重量部である、７に記載の洗浄液組成物。
９．１〜８のいずれかに記載の洗浄液組成物を用いる、重質炭化水素又は分子に極性を与える元素を含む系に生成したスラッジ及び硬質化皮膜の洗浄方法。
１０．前記洗浄液組成物を、洗浄すべきプロセス中に往復動式ポンプを用いて流通させる９に記載の洗浄方法。
１１．前記洗浄液組成物を乱流状態でスラッジ及び硬質化皮膜と接触させる９又は１０に記載の洗浄方法。
１２．前記洗浄液組成物を、０．４〜２ｍ／ｓの線速度で、洗浄すべきプロセス中に流通させる９〜１１のいずれかに記載の洗浄方法。According to the present invention, the following sludge produced in a system containing the following heavy hydrocarbon or an element that imparts polarity to molecules, a cleaning liquid composition for removing a hardened film, and the like are provided.
1. A cleaning liquid composition for removing sludge and hardened film formed in a system containing heavy hydrocarbons or elements that impart polarity to molecules, including dimethyl sulfoxide, potassium hydroxide, and water.
2. The dimethyl sulfoxide content is 10 to 85% by weight based on the total weight of the dimethyl sulfoxide, the potassium hydroxide, and the water,
The content of the potassium hydroxide is 5 to 30% by weight based on the total weight of the dimethyl sulfoxide, the potassium hydroxide, and the water,
The water content is 10 to 60% by weight based on the total weight of the dimethyl sulfoxide, the potassium hydroxide, and the water.
2. The cleaning liquid composition according to 1.
3. The dimethyl sulfoxide content is 40 to 85% by weight based on the total weight of the dimethyl sulfoxide, the potassium hydroxide, and the water,
The potassium hydroxide content is 5 to 25% by weight based on the total weight of the dimethyl sulfoxide, the potassium hydroxide, and the water,
The water content is 10 to 35% by weight based on the total weight of the dimethyl sulfoxide, the potassium hydroxide, and the water.
The cleaning liquid composition according to 1 or 2.
4). 4. The cleaning liquid composition according to any one of 1 to 3, wherein the dimethyl sulfoxide contains dimethyl sulfoxide that is recovered by distillation of a used cleaning liquid composition and reused.
5. Furthermore, the washing | cleaning liquid composition in any one of 1-4 containing alcohol.
6). The cleaning liquid composition according to 5, wherein the content of the alcohol is 1 to 10 parts by weight when the total of the dimethyl sulfoxide, the potassium hydroxide, and the water is 100 parts by weight.
7). Furthermore, the cleaning composition in any one of 1-6 containing N-methylpyrrolidone.
8). The cleaning liquid composition according to 7, wherein the content of N-methylpyrrolidone is 5 to 30 parts by weight when the total of the dimethyl sulfoxide, the potassium hydroxide, and the water is 100 parts by weight.
9. A method for cleaning sludge and hardened film produced in a system containing a heavy hydrocarbon or an element imparting polarity to molecules, using the cleaning liquid composition according to any one of 9.1 to 8.
10. 10. The cleaning method according to 9, wherein the cleaning liquid composition is circulated using a reciprocating pump during a process to be cleaned.
11. The cleaning method according to 9 or 10, wherein the cleaning liquid composition is brought into contact with sludge and a hardened film in a turbulent state.
12 The cleaning method according to any one of 9 to 11, wherein the cleaning liquid composition is circulated during a process to be cleaned at a linear velocity of 0.4 to 2 m / s.
本発明によれば、重質炭化水素又は分子に極性を与える元素を含む系に生成したスラッジ及び硬質化皮膜を除去するために有効である新規な洗浄液組成物と、それを用いた洗浄方法を提供できる。 According to the present invention, there is provided a novel cleaning liquid composition effective for removing sludge and hardened film generated in a system containing heavy hydrocarbons or elements that impart polarity to molecules, and a cleaning method using the same. Can be provided.
［洗浄液組成物］
本発明の洗浄液組成物は、重質炭化水素又は分子に極性を与える元素を含む系に生成したスラッジ及び硬質化皮膜を除去するためのものであって、ジメチルスルホキシド（ＤＭＳＯ）、水酸化カリウム（ＫＯＨ）、及び水を含む。[Cleaning liquid composition]
The cleaning liquid composition of the present invention is for removing sludge and hardened film formed in a system containing heavy hydrocarbons or elements that impart polarity to molecules, and is composed of dimethyl sulfoxide (DMSO), potassium hydroxide ( KOH), and water.
本発明の洗浄液組成物は、ジメチルスルホキシド、水酸化カリウム、及び水という特定の成分を含むことにより、従来、除去することが困難であった、重質炭化水素が存在する系に生成したスラッジ及び硬質化皮膜を除去できる。各成分が相乗的に機能することにより、有機分（油分）、無機分、塩類のほか、軽微に発錆した材料表面も同時に洗浄できる性能を有し、安定化している汚れを確実かつ効率的に除去できる。
ここで材料表面とは、例えば、プロセスを構成する機器の材料表面をいい、材料としては、例えば、炭素鋼が挙げられる。本発明の洗浄液組成物によれば、プロセス機器の材料表面に発生した、鉄錆（Ｆｅ２Ｏ３）や酸化銅（ＣｕＯ）も除去できる。The cleaning liquid composition of the present invention contains sludge produced in a system containing heavy hydrocarbons, which has been difficult to remove conventionally, by containing specific components such as dimethyl sulfoxide, potassium hydroxide, and water. Hardened film can be removed. By synergistically functioning each component, it has the ability to clean organic surfaces (oil), inorganic components, salts, and even lightly rusted material surfaces at the same time, ensuring stable and efficient contamination. Can be removed.
Here, the material surface refers to, for example, the material surface of equipment constituting the process, and examples of the material include carbon steel. According to the cleaning liquid composition of the present invention, iron rust (Fe 2 O 3 ) and copper oxide (CuO) generated on the material surface of the process equipment can also be removed.
本発明の洗浄液組成物は、重質炭化水素が存在する系に生成したスラッジ及び硬質化皮膜を除去するのに適しているが、除去できるスラッジ及び硬質化皮膜は、重質炭化水素が存在する系に生成したものだけに限定されない。重質炭化水素が存在する系では、汚れ生成の化学的要因として、例えば、炭素（Ｃ）や水素（Ｈ）の不安定な結合形態や分子全体の構造的偏り等が考えられる。 The cleaning liquid composition of the present invention is suitable for removing sludge and hardened film produced in a system in which heavy hydrocarbons are present, but the sludge and hardened film that can be removed contains heavy hydrocarbons. It is not limited only to what was generated in the system. In a system in which heavy hydrocarbons are present, for example, an unstable bond form of carbon (C) or hydrogen (H) or a structural bias of the whole molecule may be considered as a chemical factor for generating dirt.
一方、自然界の油や石炭は常に混合物であり、分子に極性を与える元素が必ず含まれる。分子に極性を与える元素とは、電気陰性度の比較的高い硫黄（Ｓ）、窒素（Ｎ）、酸素（Ｏ）等である。分子に極性を与える元素を含む化合物が存在する系では、その分子に生ずる分極性（即ち、不安定さ）が要因となり、スラッジや硬質化皮膜の汚れが生成する。分子に極性を与える元素を主鎖又は官能基に含む化合物が存在する系は、重質炭化水素が存在する系だけに限定されず、例えば、食品やバイオマス等のタンパク質が存在する系にも当てはまる。分子に極性を与える元素を含む化合物として、例えば、硫化水素、アンモニア、各種アミン等が挙げられる。 On the other hand, natural oil and coal are always a mixture and always contain elements that give polarity to molecules. Elements that give polarity to molecules include sulfur (S), nitrogen (N), oxygen (O), and the like, which have relatively high electronegativity. In a system in which a compound containing an element that imparts polarity to a molecule exists, polarizability (that is, instability) generated in the molecule is a factor, and sludge and hardened film dirt are generated. A system in which a compound containing an element that gives polarity to a molecule in a main chain or a functional group is not limited to a system in which a heavy hydrocarbon exists, and also applies to a system in which a protein such as food or biomass exists, for example. . Examples of the compound containing an element that imparts polarity to the molecule include hydrogen sulfide, ammonia, various amines, and the like.
したがって、本発明の洗浄液組成物の適用範囲は非常に広く、除去できるスラッジ及び硬質化皮膜は、特定の系に限定されない。本発明の洗浄液組成物は、少なくとも、重質炭化水素又は分子に極性を与える元素を含む系に生成したスラッジ及び硬質化皮膜を除去するためのものである。 Therefore, the application range of the cleaning liquid composition of the present invention is very wide, and the sludge and the hardened film that can be removed are not limited to a specific system. The cleaning liquid composition of the present invention is for removing sludge and hardened film produced in a system containing at least heavy hydrocarbons or elements that impart polarity to molecules.
本発明において「スラッジ及び硬質化皮膜」とは、反応、蒸留、抽出、分離、精製等の化学プロセスにおいて生じたスラッジ及び硬質化皮膜であり、例えば、複数種の炭化水素成分が結合又は重縮合した重質成分から構成されるものをいう。スラッジ及び硬質化皮膜は、発生するプロセスに依存して、重質油成分、それがさらに重縮合又はコーク化した成分、水分、炭化水素以外の硫黄や窒素を含む成分、バイオマス（動植物）等を含み得る。さらに他の成分を含んでいてもよい。 In the present invention, the term “sludge and hardened film” refers to sludge and hardened film produced in a chemical process such as reaction, distillation, extraction, separation, and purification. For example, plural kinds of hydrocarbon components are combined or polycondensed. Is composed of heavy components. Sludge and hardened coatings are composed of heavy oil components, components that are polycondensed or coked, moisture, components containing sulfur and nitrogen other than hydrocarbons, biomass (animals and plants), etc., depending on the process that occurs. May be included. Furthermore, other components may be included.
「スラッジ」は、プロセス内に堆積したり、プロセスの機器表面に付着したりした、固形の凝集物をいい、「硬質化皮膜」は、プロセスの機器表面に付着した薄膜状の硬化物をいうものとする。 “Sludge” refers to a solid agglomerate that has accumulated in the process or adhered to the equipment surface of the process, and “hardening film” refers to a thin film cured product that has adhered to the equipment surface of the process. Shall.
ジメチルスルホキシドは、スラッジ及び硬質化皮膜中の油分を溶解する。ジメチルスルホキシドは水及び油に可溶であり、水を添加することで塩の溶解性を発現する。通常、有機溶剤は、塩の溶解性を持たないが、ジメチルスルホキシドは塩の溶解性を発現し得る点で、スラッジ及び硬質化皮膜中に塩を含む場合に有利である。ジメチルスルホキシドは水に可溶であるため、スラッジ及び硬質化皮膜中に水が混入している場合でも、ジメチルスルホキシドの存在により、スラッジ及び硬質化皮膜と洗浄液組成物との接触性（濡れ性）が良好に維持される。一般に、水や蒸気（凝縮水）は、例えば化学反応プロセスを停止・開放させる際に使用されるものである。 Dimethyl sulfoxide dissolves oil in the sludge and hardened film. Dimethyl sulfoxide is soluble in water and oil, and the solubility of a salt is expressed by adding water. Usually, the organic solvent does not have salt solubility, but dimethyl sulfoxide is advantageous when salt is contained in the sludge and the hardened film in that salt solubility can be expressed. Since dimethyl sulfoxide is soluble in water, even if water is mixed in the sludge and hardened film, the contact between the sludge and hardened film and the cleaning liquid composition (wetting property) due to the presence of dimethyl sulfoxide. Is maintained well. In general, water or steam (condensed water) is used, for example, when stopping or opening a chemical reaction process.
ジメチルスルホキシドの凝固点は１９℃であり、水を添加すると０℃に低下する。したがって、本発明の洗浄液組成物は、０℃以上の周囲温度において使用することができる。本発明の洗浄液組成物は、適宜加温して用いてもよい。 Dimethyl sulfoxide has a freezing point of 19 ° C. and decreases to 0 ° C. when water is added. Therefore, the cleaning liquid composition of the present invention can be used at an ambient temperature of 0 ° C. or higher. The cleaning liquid composition of the present invention may be appropriately heated before use.
ジメチルスルホキシドの含有量は、ジメチルスルホキシド、水酸化カリウム、及び水の合計重量に対して、例えば、１０〜８５重量％であり、好ましくは４０〜８５重量％であり、より好ましくは５０〜８０重量％である。 The content of dimethyl sulfoxide is, for example, 10 to 85% by weight, preferably 40 to 85% by weight, more preferably 50 to 80% by weight based on the total weight of dimethyl sulfoxide, potassium hydroxide, and water. %.
水酸化カリウムは、後述する水に溶解して、水酸化カリウム水溶液として洗浄液組成物中に存在する。水酸化カリウムは、スラッジ及び硬質化皮膜中の油分を洗浄液組成物中に乳化する。具体的には、スラッジ及び硬質化皮膜中に含まれる分子中に極性を有する炭化水素と水酸化カリウムとの反応により、ケン化反応が起き、炭化水素骨格（構造）が維持された界面活性能を有する物質が生成される。結果として、本発明の洗浄液組成物は、スラッジ及び硬質化皮膜との馴染みが非常に良く、高い洗浄効果を発揮できる。また、水酸化カリウム水溶液は強アルカリであるため、反応性が高く、例えばスラッジ及び硬質化皮膜中の無機成分や（プロセス機器の）酸化した金属材料表面との間で化学反応を起こし、その結果、材料表面も清浄化される。さらに高濃度の水酸化カリウムはスラッジ及び硬質皮膜への浸透性が高く、材料表面からそれらを剥離させる特有の機能を持つ。 Potassium hydroxide is dissolved in water described later, and is present in the cleaning liquid composition as an aqueous potassium hydroxide solution. Potassium hydroxide emulsifies the oil in the sludge and the hardened film into the cleaning liquid composition. Specifically, a surface active ability in which a hydrocarbon skeleton (structure) is maintained by a saponification reaction caused by a reaction between hydrocarbons having polarity in molecules contained in sludge and hardened film and potassium hydroxide. Is produced. As a result, the cleaning liquid composition of the present invention is very familiar with sludge and hardened film, and can exhibit a high cleaning effect. In addition, since potassium hydroxide aqueous solution is a strong alkali, it has high reactivity. For example, it causes a chemical reaction between sludge and the inorganic component in the hardened film and the oxidized metal material surface (process equipment). The material surface is also cleaned. Furthermore, high concentration potassium hydroxide has a high permeability to sludge and hard coating, and has a specific function of peeling them from the material surface.
水酸化カリウムと水酸化ナトリウムは物性や化学特性が殆ど同じであることから、洗浄剤の分野では、従来、これらは同等のものと考えられ、水酸化ナトリウムで洗浄できない汚れは水酸化カリウムでも同様であると考えられる傾向があった。そのため、より安価な水酸化ナトリウムを使用する場合が多く、（人に対して）より危険性の高い水酸化カリウムを積極的に選択することは稀であった。 Since potassium hydroxide and sodium hydroxide have almost the same physical properties and chemical characteristics, in the field of cleaning agents, they are conventionally considered to be equivalent, and soil that cannot be cleaned with sodium hydroxide is the same with potassium hydroxide. There was a tendency to be considered. For this reason, cheaper sodium hydroxide is often used, and it is rare to actively select potassium hydroxide that is more dangerous (for humans).
しかし、本発明者らは、重質炭化水素又は分子に極性を与える元素を含む系に生成した、非常に強固なスラッジ及び硬質化皮膜、即ち、水酸化ナトリウムでは洗浄できない汚れに対して、ジメチルスルホキシドと水酸化カリウムの組み合わせが有効であることを見出した。また、洗浄対象のスラッジ及び硬質化皮膜に依存して、洗浄液組成物中の水酸化カリウムの含有量（水酸化カリウムの濃度）が重要であり、低濃度では洗浄性がない場合でも、高濃度とすればそれが発現し、かつ汚れを表面から剥離させる機能があることを見出した。 However, the inventors have found that dimethyl sulfite and hardened coatings produced in systems containing heavy hydrocarbons or molecules that polarize molecules, i.e., dirt that cannot be cleaned with sodium hydroxide, are It has been found that a combination of sulfoxide and potassium hydroxide is effective. Depending on the sludge to be cleaned and the hardened film, the content of potassium hydroxide in the cleaning liquid composition (concentration of potassium hydroxide) is important. Even if there is no detergency at low concentration, high concentration Then, it has been found that it develops and has a function of peeling off dirt from the surface.
従来は化学洗浄によりスラッジは除去できたとしても、重縮合や硫化等が複合的に起こって安定化したような硬質化皮膜までは除去できなかった。硬質化皮膜は、熱フラックスの抵抗となるため、機器材料への蓄熱を引き起こし、オーバーヒートにつながる要因ともなる。本発明の洗浄液組成物によれば、スラッジだけでなく、硬質化皮膜も除去することが可能となる。 Conventionally, even if sludge can be removed by chemical cleaning, it has not been possible to remove a hardened film that has been stabilized by polycondensation, sulfurization, or the like. Since the hardened film serves as a resistance to heat flux, it causes heat storage in the device material, which also leads to overheating. According to the cleaning liquid composition of the present invention, not only sludge but also a hardened film can be removed.
水酸化カリウムの含有量は、ジメチルスルホキシド、水酸化カリウム、及び水の合計重量に対して、例えば、５〜３０重量％であり、好ましくは５〜２５重量％であり、より好ましくは６〜２５重量％である。 The content of potassium hydroxide is, for example, 5 to 30% by weight, preferably 5 to 25% by weight, and more preferably 6 to 25% with respect to the total weight of dimethyl sulfoxide, potassium hydroxide, and water. % By weight.
水は、スラッジ及び硬質化皮膜中の塩分を溶かす。また、スラッジ及び硬質化皮膜中の水分と親和する。
水の含有量は、ジメチルスルホキシド、水酸化カリウム、及び水の合計重量に対して、例えば、１０〜６０重量％であり、好ましくは１０〜３５重量％であり、より好ましくは１４〜３５重量％である。Water dissolves the salt in the sludge and hardened film. It also has an affinity for moisture in the sludge and hardened film.
The water content is, for example, 10 to 60% by weight, preferably 10 to 35% by weight, and more preferably 14 to 35% by weight, based on the total weight of dimethyl sulfoxide, potassium hydroxide, and water. It is.
本発明の洗浄液組成物は、さらに、アルコールを含んでいてもよい。アルコールの存在により、主としてジメチルスルホキシドを含む有機相と、主として水酸化カリウムを含む水相との親和性を向上できる。また、さらに、スラッジ及び硬質化皮膜と、有機相及び水相との親和性を向上できる。 The cleaning liquid composition of the present invention may further contain alcohol. The presence of the alcohol can improve the affinity between the organic phase mainly containing dimethyl sulfoxide and the aqueous phase mainly containing potassium hydroxide. Furthermore, the affinity between the sludge and the hardened film, the organic phase and the aqueous phase can be improved.
また、本発明の洗浄液組成物を用いてスラッジ及び硬質化皮膜を洗浄する過程で、汚れ成分が洗浄され、洗浄液組成物中に溶解されるにつれ、スラッジ及び硬質化皮膜と洗浄液組成物との界面が変化して洗浄効率に影響を与える。実際に洗浄する場合、汚れが未知、油分が少ない、油分がアロマ系（芳香族化合物）の重合物である等が予想された場合は、アルコールを加えることが有効である。アルコールが存在することにより、洗浄液組成物中に溶解され分散された油分が界面化学的に安定化され（親和性向上）、その結果、油分分散が進行すると考えられる。 Further, in the process of cleaning the sludge and the hardened film using the cleaning liquid composition of the present invention, as the dirt component is washed and dissolved in the cleaning liquid composition, the interface between the sludge and the hardened film and the cleaning liquid composition Changes and affects cleaning efficiency. In the case of actual washing, it is effective to add alcohol when it is expected that the dirt is unknown, the oil content is low, or the oil content is an aroma-based (aromatic compound) polymer. It is considered that the presence of alcohol stabilizes the oil dissolved and dispersed in the cleaning liquid composition in terms of surface chemistry (improves affinity), and as a result, the oil dispersion proceeds.
アルコールとしては、例えば、炭素数１〜５の低級モノアルコール又はジオール、芳香族アルコール等が挙げられる。これらは１種を単独で用いてもよく、又は、２種以上を組み合わせて用いてもよい。好ましくは、ジオール、芳香族アルコールであり、より好ましくは、芳香族アルコールである。 Examples of the alcohol include a lower monoalcohol or diol having 1 to 5 carbon atoms, and an aromatic alcohol. These may be used individually by 1 type, or may be used in combination of 2 or more type. Preferred are diols and aromatic alcohols, and more preferred are aromatic alcohols.
アルコールの含有量は、ジメチルスルホキシド、水酸化カリウム及び水の合計を１００重量部として、例えば、１〜１０重量部であり、好ましくは３〜８重量部であり、より好ましくは５〜７重量部である。 The content of the alcohol is, for example, 1 to 10 parts by weight, preferably 3 to 8 parts by weight, more preferably 5 to 7 parts by weight, with 100 parts by weight of the total of dimethyl sulfoxide, potassium hydroxide and water. It is.
本発明の洗浄液組成物は、さらに、Ｎ−メチルピロリドンを含んでいてもよい。Ｎ−メチルピロリドンは、ジメチルスルホキシドと同様にスラッジ及び硬質化皮膜中の油分を溶解すると考えられるが、汚れ（スラッジ及び硬質化皮膜）中の重質分の割合が高いほど、その成分と親和し、洗浄速度を向上させる添加効果が認められる。
Ｎ−メチルピロリドンの含有量が、ジメチルスルホキシド、水酸化カリウム及び水の合計を１００重量部として、例えば、５〜３０重量部であり、好ましくは５〜２０重量部であり、より好ましくは１０〜１５重量部である。The cleaning liquid composition of the present invention may further contain N-methylpyrrolidone. N-methylpyrrolidone is considered to dissolve oil in sludge and hardened film in the same manner as dimethyl sulfoxide, but the higher the proportion of heavy matter in dirt (sludge and hardened film), the more the affinity for its components. In addition, the effect of adding to improve the cleaning rate is recognized.
The content of N-methylpyrrolidone is, for example, 5 to 30 parts by weight, preferably 5 to 20 parts by weight, more preferably 10 to 10 parts by weight, with the total of dimethyl sulfoxide, potassium hydroxide and water being 100 parts by weight. 15 parts by weight.
本発明の洗浄液組成物は、所定量のジメチルスルホキシド、水酸化カリウム、及び水を混合することにより調製できる。水酸化カリウムは潮解性があるため、固体ではなく、適当な濃度の水溶液（例えば、３０％水酸化カリウム溶液）を用いることが好ましい。混合する順序は特に限定されないが、例えば、水酸化カリウムを水に溶解し、得られた水酸化カリウム水溶液にジメチルスルホキシドを添加することができる。混合は、既知の任意の手段で行えばよい。 The cleaning liquid composition of the present invention can be prepared by mixing a predetermined amount of dimethyl sulfoxide, potassium hydroxide, and water. Since potassium hydroxide is deliquescent, it is preferable to use an aqueous solution (for example, a 30% potassium hydroxide solution) having an appropriate concentration instead of a solid. The order of mixing is not particularly limited. For example, potassium hydroxide can be dissolved in water, and dimethyl sulfoxide can be added to the obtained aqueous potassium hydroxide solution. Mixing may be performed by any known means.
水酸化カリウムを水溶液として扱う場合、ジメチルスルホキシドと水酸化カリウム水溶液を混合すると、ジメチルスルホキシドと水は二層に分離する。このとき水の一部がジメチルスルホキシド側に移行するので、水層中の水酸化カリウム濃度が濃縮される。
例えば、ジメチルスルホキシドと３０％水酸化カリウム水溶液を８：２の容積比で混合した場合、重量割合はジメチルスルホキシド：水酸化カリウム：水＝７７：７：１６となるが、混合により水酸化カリウム水溶液から水がジメチルスルホキシド側に引き抜かれ、水酸化カリウム水溶液層の水酸化カリウム濃度は約５０％に濃縮される。
これにより、高濃度の水酸化カリウムを含む水層が汚れに対して作用することとなり、高い洗浄効果を得ることができるとともに、危険な高濃度の水酸化カリウム水溶液をジメチルスルホキシド中に分散させることで、洗浄液全体としての安全性や取扱い性を確保することができる。When potassium hydroxide is handled as an aqueous solution, when dimethyl sulfoxide and an aqueous potassium hydroxide solution are mixed, dimethyl sulfoxide and water are separated into two layers. At this time, part of the water moves to the dimethyl sulfoxide side, so that the concentration of potassium hydroxide in the aqueous layer is concentrated.
For example, when dimethyl sulfoxide and 30% aqueous potassium hydroxide solution are mixed at a volume ratio of 8: 2, the weight ratio is dimethyl sulfoxide: potassium hydroxide: water = 77: 7: 16. Water is extracted from the dimethyl sulfoxide side, and the concentration of potassium hydroxide in the aqueous potassium hydroxide layer is concentrated to about 50%.
As a result, an aqueous layer containing a high concentration of potassium hydroxide acts on the dirt, so that a high cleaning effect can be obtained and a dangerous high concentration potassium hydroxide aqueous solution is dispersed in dimethyl sulfoxide. Therefore, the safety and handleability of the cleaning liquid as a whole can be ensured.
本発明の洗浄液組成物は、静置すると二層に分離する。上層が、主としてジメチルスルホキシドを含む有機層であり、下層が、主として水酸化カリウムを含む水層である。ジメチルスルホキシドは水親和性が非常に高いため、水層の水は有機相側に移行する。水層から有機層への水の移行が進行することにより、有機層側のジメチルスルホキシドの引火点（８９℃、タグ密閉法による）は消失し（本発明者らは、ジメチルスルホキシドと水の混合系で水が約１３重量％以上存在すると引火点が消失することを確認した。）、水層側の水酸化カリウムは、溶液の状態を維持できる最大濃度まで濃縮される。このとき、例えば、水層中の水酸化カリウム濃度は５０〜６０重量％となり、水層は、洗浄液組成物の全体積に対して、８〜１０体積％程度となる。 The cleaning liquid composition of the present invention separates into two layers upon standing. The upper layer is an organic layer mainly containing dimethyl sulfoxide, and the lower layer is an aqueous layer mainly containing potassium hydroxide. Since dimethyl sulfoxide has a very high water affinity, the water in the aqueous layer moves to the organic phase side. As the transfer of water from the water layer to the organic layer proceeds, the flash point of dimethyl sulfoxide on the organic layer side (89 ° C., by the tag sealing method) disappears (the present inventors have mixed dimethyl sulfoxide and water) It was confirmed that the flash point disappears when water is present in the system in an amount of about 13% by weight or more.) Potassium hydroxide on the aqueous layer side is concentrated to the maximum concentration that can maintain the state of the solution. At this time, for example, the concentration of potassium hydroxide in the aqueous layer is 50 to 60% by weight, and the aqueous layer is about 8 to 10% by volume with respect to the total volume of the cleaning liquid composition.
本発明の洗浄液組成物は、洗浄に用いると、スラッジ及び硬質化皮膜中の油分が洗浄液組成物中に溶解し、あるいは分散することで有機相と水相の界面状態が変化して、洗浄液組成物が二層化しなくなり、見かけ単層となってより確実にスラッジ及び硬質化皮膜に接触する性状に変化する。 When the cleaning liquid composition of the present invention is used for cleaning, the oil content in the sludge and the hardened film is dissolved or dispersed in the cleaning liquid composition, whereby the interface state between the organic phase and the aqueous phase changes, and the cleaning liquid composition The product does not become two-layered, becomes an apparent single layer, and changes to a property of contacting the sludge and the hardened film more reliably.
本発明の洗浄液組成物は、溶剤の溶媒和による油分溶解、アルカリの乳化（生成した界面活性剤にもよる）による油分分散、高濃度アルカリによる化学反応、汚れの形状崩壊と表面からの剥離、軽微な鉄錆の除去、等を１液で同時に達成できる多機能性と、汚れの種類を選ばない万能性を有する。さらに、汚れを利用して上記機能を向上できるという特異性も有している。 The cleaning liquid composition of the present invention comprises oil dissolution by solvent solvation, oil dispersion by alkali emulsification (depending on the generated surfactant), chemical reaction by high-concentration alkali, soil shape collapse and peeling from the surface, Multifunctionality that can achieve the removal of light iron rust at the same time with a single solution, and versatility regardless of the type of dirt. Furthermore, it has the peculiarity that the above functions can be improved by utilizing dirt.
一般的には、２層分離する洗浄液は扱いにくく、その使い難さから実用されることは殆どない。また、６０％程度のアルカリ剤の使用も危険性から同様である。しかしながら、本発明の洗浄液組成物は、汚れによって液がしだいに単層となり、アルカリも高濃度であるが液中に滴状で存在し、全体からみれば量は少なく、危険性もかなり低減されているといえる。 In general, a cleaning solution for separating two layers is difficult to handle and is rarely used due to its difficulty in use. The use of about 60% alkaline agent is also the same because of the danger. However, the cleaning liquid composition of the present invention gradually becomes a single layer due to dirt, and the alkali is also high in concentration, but is present in droplets in the liquid, the amount is small as a whole, and the risk is considerably reduced. It can be said that.
本発明の洗浄液組成物は、重質炭化水素系スラッジを洗浄するために使用した後に、蒸留することにより、ジメチルスルホキシドを回収して再利用することができる。即ち、本発明に洗浄液組成物に使用するジメチルスルホキシドは、使用済みの洗浄液組成物を蒸留することにより回収して再利用したジメチルスルホキシドを含んでいてもよい。
ジメチルスルホキシドの再利用により、洗浄により生ずる廃液を少なくできる。The cleaning liquid composition of the present invention can recover and reuse dimethyl sulfoxide by distillation after being used for cleaning heavy hydrocarbon sludge. That is, the dimethyl sulfoxide used in the cleaning liquid composition of the present invention may contain dimethyl sulfoxide recovered by reuse of the used cleaning liquid composition and reused.
By reusing dimethyl sulfoxide, waste liquid generated by washing can be reduced.
［洗浄液組成物を用いた洗浄方法］
本発明の洗浄方法は、重質炭化水素油が存在する系に生成したスラッジ及び硬質化皮膜の洗浄方法であって、前記説明した本発明の洗浄液組成物を用いるものである。本発明の洗浄液組成物を用いて洗浄することにより、一般に洗浄が極めて困難で安定化しているスラッジ及び硬質化皮膜を確実かつ効率的に除去できる。[Cleaning method using cleaning liquid composition]
The cleaning method of the present invention is a method for cleaning sludge and hardened film produced in a system in which a heavy hydrocarbon oil is present, and uses the above-described cleaning liquid composition of the present invention. By washing with the cleaning liquid composition of the present invention, sludge and hardened coating that are generally extremely difficult to wash and stabilized can be removed reliably and efficiently.
洗浄は、具体的には、洗浄すべきプロセス中に本発明の洗浄液組成物を流通させればよい。プロセス中に洗浄液組成物を流通させることにより、機器の内部表面に固着するスラッジ及び硬質化皮膜に洗浄液組成物を接触させることができる。ウォータージェット洗浄等の物理洗浄では、機器内部の構造により、ジェットが届きにくかったり、当たりが弱くなったりすると、スラッジや硬質化皮膜を確実には洗浄できないが、本発明の洗浄方法によれば、物理洗浄より機器内部の構造による影響を受けにくい。 Specifically, the cleaning may be performed by distributing the cleaning liquid composition of the present invention during the process to be cleaned. By flowing the cleaning liquid composition during the process, the cleaning liquid composition can be brought into contact with the sludge and the hardened film that adhere to the inner surface of the device. In physical cleaning such as water jet cleaning, the sludge and the hardened film cannot be cleaned reliably if the jet is difficult to reach due to the internal structure of the device, or if the contact becomes weak, but according to the cleaning method of the present invention, Less affected by internal structure than physical cleaning.
本発明の洗浄方法では、洗浄液組成物を乱流状態でスラッジ及び硬質化皮膜と接触させることが好ましい。さらに液の循環には圧力が変動する往復動式ポンプを使用することが好ましい。これは液による汚れのいわばハンマリング効果を狙ったものであり、より効率的に洗浄できるためである。
また、本発明の洗浄方法では、洗浄液組成物を、例えば０．４〜２ｍ／ｓ、好ましくは０．４〜１ｍ／ｓ、より好ましくは１ｍ／ｓの線速度で、洗浄すべきプロセス中に流通させることが好ましい。これにより、より確実・効率的に洗浄できる。In the cleaning method of the present invention, the cleaning liquid composition is preferably brought into contact with the sludge and the hardened film in a turbulent state. Furthermore, it is preferable to use a reciprocating pump whose pressure varies for the circulation of the liquid. This is because a so-called hammering effect of dirt due to the liquid can be achieved and cleaning can be performed more efficiently.
In the cleaning method of the present invention, the cleaning liquid composition is applied during the process to be cleaned at a linear velocity of, for example, 0.4 to 2 m / s, preferably 0.4 to 1 m / s, more preferably 1 m / s. It is preferable to circulate. Thereby, it can wash | clean more reliably and efficiently.
本発明の洗浄液組成物は、静置すると二層に分離するが、循環洗浄に使用するポンプ吸入ライン端位置を適正化することにより、水酸化カリウムを含む重い水相を滴状として洗浄液組成物全体に分散させることができる。水相においては水酸化カリウムが濃縮されており、この高濃度の水酸化カリウムが洗浄の開始剤あるいは促進剤として機能する。さらに、ジメチルスルホキシド、水、及び任意成分のそれぞれの機能が相乗的に働く。その結果、従来全く洗浄できなかった汚れ（特に硫黄や炭素からなる硬質化皮膜）が除去できるようになる。 The cleaning liquid composition of the present invention separates into two layers when allowed to stand, but by optimizing the position of the end of the pump suction line used for circulating cleaning, the cleaning liquid composition forms a heavy aqueous phase containing potassium hydroxide as drops. Can be dispersed throughout. In the aqueous phase, potassium hydroxide is concentrated, and this high concentration of potassium hydroxide functions as a washing initiator or accelerator. Further, the functions of dimethyl sulfoxide, water, and optional components work synergistically. As a result, dirt (especially hardened film made of sulfur or carbon) that could not be cleaned at all can be removed.
洗浄を続けると、スラッジ及び硬質化皮膜中の油分が洗浄液組成物中に溶解し、分散することにより、界面が変化して、洗浄液組成物が二層化しなくなり、見かけ単層となってより確実にスラッジ及び硬質化皮膜に接触する性状に変化する。 If cleaning is continued, the oil in the sludge and hardened film dissolves and disperses in the cleaning liquid composition, so that the interface changes and the cleaning liquid composition does not become two-layered. It changes to the property of contacting sludge and hardened film.
以下、実施例により、本発明をさらに具体的に説明するが、本発明はこれらの実施例に限定されない。
試験例１
１年間の運転を経てＣＯＧ精製プラント実機に付着した汚れ（スラッジと硬質皮膜を含む）を物理的に採取し、トルエンを用いて処理した。具体的には、汚れを５０倍量のトルエン中に添加し、３０分間超音波処理したのち、ろ過して得られた残渣を乾燥した。トルエンによる処理で溶解しない残渣を、表１に示す種々の洗浄液組成物で洗浄し、洗浄特性を評価した。洗浄は、スラッジ残渣を、洗浄液組成物を入れた容器に浸漬し、室温で容器を２時間振とうすることにより行った。結果を表１に示す。EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to these Examples.
Test example 1
Dirt (including sludge and hard coating) adhering to the actual COG refinery plant after one year of operation was physically collected and treated with toluene. Specifically, the soil was added to 50 times the amount of toluene, subjected to ultrasonic treatment for 30 minutes, and then the residue obtained by filtration was dried. Residues not dissolved by the treatment with toluene were washed with various cleaning liquid compositions shown in Table 1, and the washing characteristics were evaluated. Cleaning was performed by immersing the sludge residue in a container containing the cleaning liquid composition and shaking the container at room temperature for 2 hours. The results are shown in Table 1.
洗浄特性は、濡れ性、溶解性、分散性、洗浄性を定性的に評価し、「効果が顕著である」を＋＋＋、「効果がある」を＋＋、「効果がわずかにある」を＋、「効果がみられない」を−とした。
濡れ性は、洗浄液組成物と汚れ（スラッジ及び硬質化皮膜）との接触性である。
溶解性は、洗浄液組成物による汚れ（スラッジ及び硬質化皮膜）を溶解する能力である。
分散性は、洗浄液組成物中に汚れ（スラッジ及び硬質化皮膜）を分散させる能力である。
洗浄性は、付着した汚れ（スラッジ及び硬質化皮膜）を洗浄して落とす能力であり、溶解性と分散性を足し合わせた特性である。The cleaning characteristics are qualitatively evaluated for wettability, solubility, dispersibility, and detergency, and “effective” is ++, “effective” is ++, “slightly effective” is +, “No effect” was defined as “−”.
The wettability is the contact property between the cleaning liquid composition and dirt (sludge and hardened film).
Solubility is the ability to dissolve dirt (sludge and hardened film) due to the cleaning liquid composition.
Dispersibility is the ability to disperse dirt (sludge and hardened film) in the cleaning liquid composition.
Detergency is the ability to wash off and remove attached dirt (sludge and hardened film), and is a characteristic that combines solubility and dispersibility.
一般的な有機溶媒であるトルエンは油分を溶解除去する効果があると考えられる。トルエンによっても洗浄（溶解）されない強固な汚れ（残渣）に対して、実施例１の洗浄剤組成物はすぐれた洗浄特性を示した。 It is considered that toluene, which is a general organic solvent, has an effect of dissolving and removing oil. The cleaning composition of Example 1 showed excellent cleaning properties against strong soils (residues) that were not cleaned (dissolved) by toluene.
試験例２
１年間の運転を経てＣＯＧ精製プラント実機に付着した汚れ（スラッジと硬質皮膜を含む）を物理的に採取し、表２に示す種々の洗浄液組成物で洗浄し、洗浄特性を評価した。洗浄は、実機から採取した汚れをガラス製容器の壁面に付着させた後、洗浄液組成物を入れ、室温で容器を２時間振とうすることにより行った。結果を表２に示す。
洗浄特性の評価は、試験例１と同様に行った。Test example 2
Dirt (including sludge and hard coating) adhering to the actual COG refinery plant after one year of operation was physically collected, washed with various cleaning liquid compositions shown in Table 2, and the cleaning characteristics were evaluated. Washing was performed by adhering the dirt collected from the actual machine to the wall surface of the glass container, and then putting the cleaning liquid composition and shaking the container at room temperature for 2 hours. The results are shown in Table 2.
Evaluation of the cleaning characteristics was performed in the same manner as in Test Example 1.
実施例２の洗浄液組成物は、トルエンで処理していない油分を含む汚れに対しても、すぐれた洗浄特性を示した。
比較例２の洗浄液組成物は、同様にすぐれた洗浄特性を示した。しかし、ジメチルスルホキシドは凝固点が１９℃であるため、洗浄の周囲環境の温度に制約があり、適用が制限されてしまう。また、後述する試験例３の比較例５では、汚れの再付着がみられた。
比較例３の洗浄液組成物は、洗浄後の洗浄液に呈色がみられ、溶解性（又は乳化分散性）にわずかに効果がみられたが、総合的な洗浄特性はすぐれた効果は得られなかった。The cleaning liquid composition of Example 2 showed excellent cleaning properties even against soils containing oil not treated with toluene.
The cleaning liquid composition of Comparative Example 2 showed excellent cleaning characteristics as well. However, since dimethyl sulfoxide has a freezing point of 19 ° C., there are restrictions on the temperature of the environment surrounding the cleaning, and its application is limited. In Comparative Example 5 of Test Example 3 to be described later, redeposition of dirt was observed.
In the cleaning liquid composition of Comparative Example 3, color was observed in the cleaning liquid after cleaning, and a slight effect was observed in solubility (or emulsification dispersibility), but an excellent effect in overall cleaning characteristics was obtained. There wasn't.
試験例３
１年間の運転を経てＣＯＧ精製プラント実機に付着した汚れ（スラッジと硬質皮膜を含む）を物理的に採取し、表３に示す種々の洗浄液組成物で洗浄し、洗浄特性を評価した。洗浄は、実機から採取した汚れ９０ｍｇをガラス製容器の壁面に付着させた後、洗浄液組成物５ｍｌを入れ、室温で容器を２時間振とうすることにより行った。Test example 3
Dirt (including sludge and hard coating) adhering to the actual COG refinery plant after one year of operation was physically collected, washed with various cleaning liquid compositions shown in Table 3, and the cleaning characteristics were evaluated. Washing was performed by adhering 90 mg of dirt collected from the actual machine to the wall surface of the glass container, and then adding 5 ml of the cleaning liquid composition and shaking the container at room temperature for 2 hours.
洗浄後に洗浄液中に分散した固形分をろ過、秤量し、分散分（重量％）とした。
洗浄後に容器壁面に付着している固形物を秤量し、残留分（重量％）とした。残留分は、洗浄開始前から洗浄後まで容器壁面に付着したままの固形物と、洗浄により一旦洗浄液中に分散したものの容器壁面に再付着した固形物を含む。
洗浄前の汚れから分散分と残留分を控除したものを、溶解分（重量％）とした。
分散分と溶解分とを加算して、洗浄分（重量％）とした。
ろ過後に容器を水洗して、水洗性を評価した。
結果を表３に示す。After washing, the solid content dispersed in the washing liquid was filtered and weighed to obtain a dispersion (% by weight).
The solid matter adhering to the wall surface of the container after washing was weighed to obtain a residue (% by weight). The residue includes solids that remain attached to the container wall surface from before the start of cleaning to after cleaning, and solids that have been once dispersed in the cleaning liquid by cleaning and reattached to the container wall surface.
A product obtained by subtracting the dispersion and the residue from the soil before washing was defined as a dissolved content (% by weight).
The dispersion and the dissolved component were added to obtain a washing component (% by weight).
After filtration, the container was washed with water, and the washability was evaluated.
The results are shown in Table 3.
実施例３〜５の洗浄液組成物は、いずれも洗浄効果を示した。なかでも実施例５の洗浄液組成物は、すべての汚れを溶解ないし分散して洗浄した。また、水洗性も良好で、溶解した油分や固形物が水洗により再び壁面に再付着して表面を汚すことはなかった。
比較例４の洗浄液組成物は、汚れの濡れ性が乏しく、洗浄効果が得られなかった。
比較例５の洗浄液組成物は、水洗により汚れの析出がみられた。The cleaning liquid compositions of Examples 3 to 5 all showed a cleaning effect. In particular, the cleaning liquid composition of Example 5 was cleaned by dissolving or dispersing all the soils. Moreover, the water washability was also good, and the dissolved oil and solid matter did not adhere again to the wall surface by washing with water, and the surface was not soiled.
The cleaning liquid composition of Comparative Example 4 had poor soil wettability, and no cleaning effect was obtained.
In the cleaning liquid composition of Comparative Example 5, precipitation of dirt was observed by washing with water.
プラント実機において洗浄を行う際、洗浄に用いた洗浄液全てを排水することは事実上不可能であり、洗浄後にはある程度の量の洗浄液がプラント実機内に残留し、この残留液を含む状態で次の工程である水洗を行うのが通常である。本試験例では、洗浄液による洗浄後に容器内から洗浄液を抜いたが、容器の壁面や底面に僅かに洗浄液が残留した状態で水洗を行い、水洗性を評価した。比較例５では、汚れのすべてを洗浄液中に溶解又は分散できていたが、その後の水洗により、容器内に残留した僅かな洗浄液中に溶解していた汚れ油分が、溶解状態を保てなくなり、容器の壁面に再付着する様子が観察された。 When cleaning in the actual plant, it is practically impossible to drain all of the cleaning liquid used for cleaning, and after cleaning, a certain amount of cleaning liquid remains in the actual plant and contains the residual liquid. It is usual to perform the water washing which is the process. In this test example, the cleaning liquid was removed from the container after cleaning with the cleaning liquid, but the cleaning was performed with the cleaning liquid remaining slightly on the wall surface and bottom surface of the container, and the water cleaning property was evaluated. In Comparative Example 5, all of the dirt could be dissolved or dispersed in the cleaning liquid, but the subsequent washing with water, the dirty oil dissolved in the slight cleaning liquid remaining in the container could not maintain the dissolved state, The appearance of reattachment to the wall of the container was observed.
実施例６
１年間の運転を経たＣＯＧ精製プラント実機のプロセス内に、ジメチルスルホキシド（蒸留再生物を含む）：水酸化カリウム：水＝７７：７：１６（重量基準）の組成の洗浄液組成物を張り込み、室温で一晩浸漬した。その後、５０℃以下で１５時間、往復動ポンプを使って流通させた。洗浄液組成物の線速度は０．４〜１．０ｍ／ｓとした。
洗浄液組成物の流通後、水を流通させて水洗を行ったうえでプロセスの機器を開放し、汚れ（スラッジ及び硬質化皮膜）が固着していないことを確認した。Example 6
A cleaning liquid composition having a composition of dimethyl sulfoxide (including distilled regenerated product): potassium hydroxide: water = 77: 7: 16 (by weight) was put into the actual process of the COG purification plant after one year operation, and the room temperature Soaked overnight. Then, it was made to distribute | circulate using a reciprocating pump for 15 hours at 50 degrees C or less. The linear velocity of the cleaning liquid composition was 0.4 to 1.0 m / s.
After circulation of the cleaning liquid composition, water was circulated and washed with water, and then the process equipment was opened, and it was confirmed that dirt (sludge and hardened film) was not fixed.
試験例４
ジメチルスルホキシド：水酸化カリウム：水＝７７：７：１６（重量基準）の組成の洗浄液組成物（実施例７）と、ジメチルスルホキシド：水酸化カリウム：水：Ｎ−メチルピロリドン＝６２：７：１６：１５（重量基準）の組成の洗浄液組成物（実施例８）とを用いて、洗浄試験を行った。
具体的には、１年間の運転を経て重質油精製プラント実機に付着した汚れ（スラッジと硬質皮膜を含む）を物理的に採取し、２０ｍＬのサンプル瓶に入れた。このサンプル瓶を減圧加温（１ｍｍＨｇ、１６０℃）下に置き、汚れ上面を平滑に成形してから、汚れの重量（Ｗ０）を測定した。汚れ上面を平滑にしたのは、後の洗浄性の比較において汚れの接液表面の違いをなくして洗浄液組成物の違いによる評価をするためである。
次いで、サンプル瓶に洗浄液組成物１０ｍＬを入れ、室温下、２００ｒｐｍで、一定時間、サンプル瓶を振とうすることにより洗浄してから洗浄液を抜き出し、残留した汚れの重量（Ｗｔ）を測定し、汚れ除去率（重量％）＝（１−Ｗｔ／Ｗ０）×１００を算出した。
次いで、抜き出した洗浄液を再びサンプル瓶に戻し、洗浄を行い、汚れ除去率の経時的な変化を比較して洗浄性を評価した。
実施例７、８の洗浄液組成物はともに良好な洗浄性を示した。Ｎ−メチルピロリドンを含む実施例７の洗浄液組成物は、Ｎ−メチルピロリドンを含まない実施例８の洗浄液組成物に比べて、汚れの除去に要する時間が短く、高い洗浄性を示した。Test example 4
A cleaning liquid composition (Example 7) having a composition of dimethyl sulfoxide: potassium hydroxide: water = 77: 7: 16 (weight basis) and dimethyl sulfoxide: potassium hydroxide: water: N-methylpyrrolidone = 62: 7: 16 A cleaning test was conducted using a cleaning liquid composition (Example 8) having a composition of 15 (weight basis).
Specifically, the dirt (including sludge and hard coating) adhering to the actual heavy oil refinery plant after one year of operation was physically collected and placed in a 20 mL sample bottle. The sample bottle was placed under reduced pressure heating (1 mmHg, 160 ° C.), the upper surface of the soil was formed smoothly, and the weight of the soil (W 0 ) was measured. The reason for making the upper surface of the soil smooth is to eliminate the difference in the wetted surface of the soil in the subsequent comparison of the cleaning properties, and to make an evaluation based on the difference in the cleaning liquid composition.
Next, 10 mL of the cleaning solution composition is placed in the sample bottle, and the sample solution is washed by shaking the sample bottle at room temperature at 200 rpm for a certain period of time. Then, the cleaning solution is extracted, and the weight (W t ) of the remaining dirt is measured. Dirt removal rate (% by weight) = (1−W t / W 0 ) × 100 was calculated.
Subsequently, the extracted cleaning liquid was returned to the sample bottle again, and cleaning was performed. The cleaning property was evaluated by comparing changes with time of the soil removal rate.
The cleaning liquid compositions of Examples 7 and 8 both showed good cleaning properties. The cleaning liquid composition of Example 7 containing N-methylpyrrolidone had a shorter cleaning time and higher cleaning properties than the cleaning liquid composition of Example 8 containing no N-methylpyrrolidone.
本発明の洗浄液組成物及び洗浄方法は、重質炭化水素又は分子に極性を与える元素を含む系に生成したスラッジ及び硬質化皮膜を洗浄するために使用できる。特に、コークス炉ガス精製プロセスに好適に適用できるが、他の種々のプロセスにも適用できる。 The cleaning liquid composition and cleaning method of the present invention can be used to clean sludge and hardened coatings produced in systems containing heavy hydrocarbons or elements that impart polarity to molecules. In particular, it can be suitably applied to a coke oven gas purification process, but can also be applied to various other processes.
上記に本発明の実施形態及び／又は実施例を幾つか詳細に説明したが、当業者は、本発明の新規な教示及び効果から実質的に離れることなく、これら例示である実施形態及び／又は実施例に多くの変更を加えることが容易である。従って、これらの多くの変更は本発明の範囲に含まれる。
この明細書に記載の文献及び本願のパリ優先の基礎となる日本出願明細書の内容を全てここに援用する。Although several embodiments and / or examples of the present invention have been described in detail above, those skilled in the art will appreciate that these exemplary embodiments and / or embodiments are substantially without departing from the novel teachings and advantages of the present invention. It is easy to make many changes to the embodiment. Accordingly, many of these modifications are within the scope of the present invention.
The contents of the documents described in this specification and the specification of the Japanese application that is the basis of Paris priority of the present application are all incorporated herein.
Claims (12)
前記水酸化カリウムの含有量が、前記ジメチルスルホキシド、前記水酸化カリウム、及び前記水の全重量に対して、５〜３０重量％であり、
前記水の含有量が、前記ジメチルスルホキシド、前記水酸化カリウム、及び前記水の全重量に対して、１０〜６０重量％である、
請求項１に記載の洗浄液組成物。The dimethyl sulfoxide content is 10 to 85% by weight based on the total weight of the dimethyl sulfoxide, the potassium hydroxide, and the water,
The content of the potassium hydroxide is 5 to 30% by weight based on the total weight of the dimethyl sulfoxide, the potassium hydroxide, and the water,
The water content is 10 to 60% by weight based on the total weight of the dimethyl sulfoxide, the potassium hydroxide, and the water.
The cleaning liquid composition according to claim 1.
前記水酸化カリウムの含有量が、前記ジメチルスルホキシド、前記水酸化カリウム、及び前記水の全重量に対して、５〜２５重量％であり、
前記水の含有量が、前記ジメチルスルホキシド、前記水酸化カリウム、及び前記水の全重量に対して、１０〜３５重量％である、
請求項１又は２に記載の洗浄液組成物。The dimethyl sulfoxide content is 40 to 85% by weight based on the total weight of the dimethyl sulfoxide, the potassium hydroxide, and the water,
The potassium hydroxide content is 5 to 25% by weight based on the total weight of the dimethyl sulfoxide, the potassium hydroxide, and the water,
The water content is 10 to 35% by weight based on the total weight of the dimethyl sulfoxide, the potassium hydroxide, and the water.
The cleaning liquid composition according to claim 1 or 2.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05278041A (en) * | 1992-03-31 | 1993-10-26 | Hoya Corp | Polyurethane remover |
| JPH0943253A (en) * | 1995-08-03 | 1997-02-14 | Olympus Optical Co Ltd | Cleaning device for medical analyzer |
| JP2011164293A (en) * | 2010-02-08 | 2011-08-25 | Tokyo Ohka Kogyo Co Ltd | Cleaning solution for lithography and method for forming wiring line |
| JP2013169490A (en) * | 2012-02-17 | 2013-09-02 | Hitachi Koki Co Ltd | High pressure washing device |
| JP2014205758A (en) * | 2013-04-12 | 2014-10-30 | コーデックケミカル株式会社 | Cleaning agent composition, cleaning agent comprising the same, and cleaning method using those |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10219296A (en) * | 1997-02-13 | 1998-08-18 | Ito Kogaku Kogyo Kk | Removal of laminated coating film of organic optical element |
| JP4598987B2 (en) * | 2001-05-29 | 2010-12-15 | 三井化学株式会社 | Method for removing adhered polymer |
-
2017
- 2017-01-20 WO PCT/JP2017/001921 patent/WO2017126652A1/en active Application Filing
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05278041A (en) * | 1992-03-31 | 1993-10-26 | Hoya Corp | Polyurethane remover |
| JPH0943253A (en) * | 1995-08-03 | 1997-02-14 | Olympus Optical Co Ltd | Cleaning device for medical analyzer |
| JP2011164293A (en) * | 2010-02-08 | 2011-08-25 | Tokyo Ohka Kogyo Co Ltd | Cleaning solution for lithography and method for forming wiring line |
| JP2013169490A (en) * | 2012-02-17 | 2013-09-02 | Hitachi Koki Co Ltd | High pressure washing device |
| JP2014205758A (en) * | 2013-04-12 | 2014-10-30 | コーデックケミカル株式会社 | Cleaning agent composition, cleaning agent comprising the same, and cleaning method using those |
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| WO2017126652A1 (en) | 2017-07-27 |
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