JPH09241636A - Oil-soluble filmy corrosion preventing agent and corrosion prevention of metallic surface using the same - Google Patents
Oil-soluble filmy corrosion preventing agent and corrosion prevention of metallic surface using the sameInfo
- Publication number
- JPH09241636A JPH09241636A JP5196196A JP5196196A JPH09241636A JP H09241636 A JPH09241636 A JP H09241636A JP 5196196 A JP5196196 A JP 5196196A JP 5196196 A JP5196196 A JP 5196196A JP H09241636 A JPH09241636 A JP H09241636A
- Authority
- JP
- Japan
- Prior art keywords
- corrosion
- oil
- compound
- mgkoh
- preventing agent
- Prior art date
- Legal status (The legal status 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 status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、金属表面、特に石
油精製、石油化学プラントなどの各種炭化水素処理装置
における金属表面の腐食を防止するための油溶性皮膜性
腐食防止剤およびそれを用いてなる金属表面の腐食防止
方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oil-soluble film-forming corrosion inhibitor for preventing corrosion of a metal surface, particularly a metal surface in various hydrocarbon treatment equipment such as petroleum refining and petrochemical plants. The present invention relates to a method for preventing corrosion of a metal surface.
【０００２】[0002]
【従来の技術】炭化水素処理装置、具体的には石油精
製、石油化学プラントにおける各種装置において、装置
内のプロセス側には原料あるいは製品である炭化水素油
が多くの水分と共存する場合が多くある。その典型的な
例が原油常圧蒸留塔であり、原油が持ち込んだ水分、原
油脱塩に用いた洗浄水の残り、さらに塔内へのスチーム
吹き込みによって多量の水が存在している。このように
水が装置内で炭化水素油と共存する場合には水溶性物
質、例えば塩酸などを溶け込むので、腐食性は極めて高
くなる。2. Description of the Related Art In hydrocarbon treatment equipment, specifically various equipment in petroleum refining and petrochemical plants, hydrocarbon oil as a raw material or a product often coexists with a large amount of water on the process side of the equipment. is there. A typical example thereof is a crude oil atmospheric distillation column, in which water brought in by crude oil, residual washing water used for desalting crude oil, and a large amount of water due to steam blowing into the tower are present. Thus, when water coexists with hydrocarbon oil in the apparatus, it dissolves a water-soluble substance such as hydrochloric acid, so that the corrosiveness becomes extremely high.
【０００３】原油常圧蒸留塔の場合、原油は地中から採
掘したときから各種塩類が含まれており、蒸留前に脱塩
処理をしても完全に除くことは実質不可能で、結局これ
ら塩類が蒸留塔に持ち込まれることとなる。原油中に混
入している塩類としては、塩化マグネシウム、塩化カル
シウム、塩化ナトリウムが多く、蒸留塔に持ち込まれる
と塔内、特に塔底部の高温によって熱分解し塩化水素を
発生する。蒸留塔塔頂部では温度が次第に下がり、それ
に伴って水分が凝縮し、この凝縮水中に塔内で生じた塩
化水素などの腐食性物質が溶解していく。特に凝縮初期
では僅かな量の水に多量の腐食性物質が溶け込むので極
めて腐食性が大である。この腐食は一般に、初期凝縮腐
食と呼ばれ、種々の腐食対策がとられてきた。代表的な
腐食対策は、アミン類を主成分とする中和性腐食防止剤
によって凝縮水分のｐＨを上昇させて腐食抑制を図る方
法と、油溶性皮膜性腐食防止剤を用いて金属表面に有機
皮膜を形成し、金属と凝縮水を隔絶させることによって
腐食抑制を図る方法（例えば、特公昭５３−２２５３２
号公報）があり、両者の併用が多く行われている。In the case of a crude oil atmospheric distillation column, crude oil contains various salts even when it is mined from the ground, and it is virtually impossible to completely remove it even by desalting before distillation. Salts will be brought into the distillation column. Most of the salts mixed in the crude oil are magnesium chloride, calcium chloride and sodium chloride, and when they are brought into a distillation column, they are thermally decomposed due to the high temperature inside the column, especially at the bottom of the column to generate hydrogen chloride. At the top of the distillation column, the temperature gradually decreases, and along with this, water is condensed, and corrosive substances such as hydrogen chloride generated in the column are dissolved in the condensed water. Particularly in the initial stage of condensation, a large amount of corrosive substance is dissolved in a small amount of water, so that it is extremely corrosive. This corrosion is generally called initial condensation corrosion, and various corrosion countermeasures have been taken. Typical measures against corrosion include a method of increasing the pH of condensed water with a neutralizing corrosion inhibitor containing amines as a main component to suppress corrosion, and an organic solvent on the metal surface using an oil-soluble film corrosion inhibitor. A method for preventing corrosion by forming a film and isolating the metal and condensed water (for example, Japanese Patent Publication No. 53-22532).
No.), and both are often used in combination.
【０００４】中和性腐食防止剤は、凝縮水のｐＨを中性
から弱塩基性に保つ量が注入され、生成した中和塩はプ
ロセス水と共に製品油から分離される。一方、油溶性皮
膜性腐食防止剤は、金属表面に薄い皮膜を作るがこの皮
膜は金属表面に化学平衡で吸着されているもので、炭化
水素油中に常にある濃度保たれていることが必要であ
る。従って油溶性皮膜性腐食防止剤は製品である炭化水
素油に含まれたまま製品に、あるいは後続装置に行くの
で、製品、あるいは後続装置で悪い影響がないことが必
要条件である。製品への影響として重要な項目の一つ
に、水分離指数〔Ｗａｔｅｒ Ｓｅｐａｒａｔｉｏｎ Ｉ
ｎｄｅｘ，Ｍｅｔｈｏｄ(ＷＳＩＭ)、またはＭｏｄｉｆ
ｉｅｄ Ｍｉｃｒｏ Ｓｅｐａｒａｔｉｏｎ Ｓｕｒｆａ
ｃｔａｎｔｓ（ＭＳＥＰ）；ＪＩＳ Ｋ−２２７６〕が
ある。油溶性皮膜性腐食防止剤が金属表面に薄い皮膜を
作り水を隔絶させるためには、分子内に金属に吸着する
基と、親炭化水素基とをもつように分子設計することで
ある。金属に吸着する基は親水性であるので、炭化水素
油中に油溶性皮膜性防食剤が入ったとき、これが界面活
性剤として作用し、該油と水の分離を悪くするように作
用する懸念がある。従って、油溶性皮膜性腐食防止剤と
しては、出来る限り少量の添加で本来の腐食防止効果を
発揮し、その添加量で水分離が悪くならないことが要求
される。航空ガソリン、航空タービン燃料油などでは、
水分離指数が特に重要な管理項目である。The neutralizing corrosion inhibitor is injected in an amount to keep the pH of the condensed water from neutral to weakly basic, and the neutralized salt formed is separated from the product oil together with the process water. On the other hand, the oil-soluble film-forming corrosion inhibitor forms a thin film on the metal surface, but this film is adsorbed to the metal surface in chemical equilibrium, and it is necessary to maintain a certain concentration in the hydrocarbon oil. Is. Therefore, the oil-soluble film-forming corrosion inhibitor goes to the product as it is contained in the hydrocarbon oil as a product or to the subsequent device, so that it is a necessary condition that there is no adverse effect on the product or the subsequent device. One of the important items affecting the product is the water separation index [Water Separation I].
index, Method (WSIM), or Modif
ied Micro Separation Surfa
ctants (MSEP); JIS K-2276]. In order for the oil-soluble film-forming corrosion inhibitor to form a thin film on the metal surface and isolate water, it is necessary to design the molecule so that it has a group adsorbing to the metal and a parent hydrocarbon group in the molecule. Since the group adsorbed on the metal is hydrophilic, when an oil-soluble film-forming anticorrosive agent is contained in the hydrocarbon oil, it acts as a surfactant, which may deteriorate the separation of the oil and water. There is. Therefore, as the oil-soluble film-forming corrosion inhibitor, it is required that the original corrosion-inhibiting effect is exhibited by adding as little as possible, and the water separation is not deteriorated by the addition amount. For aviation gasoline, aviation turbine fuel oil, etc.,
The water separation index is a particularly important control item.
【０００５】油溶性皮膜性腐食防止剤は化学構造上、金
属に吸着する基と親炭化水素基とが同一分子中にあり、
分子の一部が金属表面に吸着し、その上に親炭化水素基
が並び炭化水素油を取り込みんで炭化水素油の皮膜を形
成させようとするものである。このような思想に適合し
た油溶性皮膜性腐食防止剤の例を挙げると、イミダゾリ
ン環を有したものでは、ジエチレントリアミンとナフテ
ン酸とを反応させて生成したイミダゾリン化合物を作用
成分としてなる組成物を石油精製系の頂部蒸気管路中に
注入する方法（特開昭４９−３６５５１号公報）があ
る。この場合イミダゾリン環は分子中に１つであり、 一
般式（II）のように表される。Due to the chemical structure, the oil-soluble film-forming corrosion inhibitor has a group adsorbing to a metal and a parent hydrocarbon group in the same molecule,
Part of the molecule is adsorbed on the metal surface, and the parent hydrocarbon group is arranged on the metal surface to take in the hydrocarbon oil and form a film of the hydrocarbon oil. To give an example of an oil-soluble film-forming corrosion inhibitor suitable for such an idea, a compound having an imidazoline ring may be used as a petroleum composition containing an imidazoline compound produced by reacting diethylenetriamine and naphthenic acid. There is a method (Japanese Patent Laid-Open No. 49-36551) of injecting into the top steam line of the refining system. In this case, there is one imidazoline ring in the molecule, which is represented by the general formula (II).
【０００６】[0006]
【化２】 Embedded image
【０００７】〔但し、式中Ｒ4およびＲ5はそれぞれ同一
あるいは異なるナフテン酸残基を示す〕[Wherein R 4 and R 5 represent the same or different naphthenic acid residues]
【０００８】最近、石油精製、石油化学プラントなど炭
化水素処理装置においては、経済的、および資源的な制
約から原料に性状の悪いものを使わざるをえなくなり、
装置内の腐食環境が悪化し、また運転条件の変更もあっ
て、より厳しい腐食管理が求められるようになった。現
状では、装置内での腐食環境の悪化に対して従来の腐食
防止剤の注入量増加ということで対処しているが、装置
内のファウリング（汚れ）の発生、石油製品の性状とし
て水分離指数の悪化などの問題を引き起こす可能性があ
り、注入量増加による対処には自ずと限界がある。Recently, in hydrocarbon processing equipment such as petroleum refining and petrochemical plants, it has been unavoidable to use raw materials having bad properties due to economical and resource constraints.
As the corrosive environment inside the equipment deteriorated and the operating conditions changed, stricter corrosion control became necessary. Currently, we are dealing with the deterioration of the corrosive environment in the equipment by increasing the injection amount of the conventional corrosion inhibitor, but fouling (dirt) in the equipment, water separation as a property of petroleum products It may cause problems such as deterioration of the index, and there is a natural limit to dealing with the increase in injection amount.
【０００９】[0009]
【発明が解決しようとする課題】油溶性皮膜性腐食防止
剤は極力少ない添加量で、より大きな腐食防止効果を要
求される。本発明の目的は、少量添加で安定な腐食防御
皮膜を形成し、併せて水分離性に優れた油溶性皮膜性腐
食防止剤、およびそれを作用してなる金属表面の腐食防
止方法を提供することにある。The oil-soluble film-forming corrosion inhibitor is required to have a greater corrosion-inhibiting effect with a minimum addition amount. An object of the present invention is to provide an oil-soluble film-forming corrosion inhibitor which forms a stable corrosion protection film even when added in a small amount, and is also excellent in water separation property, and a method for preventing corrosion of a metal surface which acts on it. Especially.
【００１０】[0010]
【課題を解決するための手段】本発明者らは、油溶性皮
膜性腐食防止剤の親炭化水素基と金属に吸着する基につ
いて系統的な研究を行った結果、特定の構造のイミダゾ
リン化合物を用いることにより極めて効率よく腐食の抑
制ができることを見いだし、本発明をなすに至った。[Means for Solving the Problems] The present inventors have conducted a systematic study on the parent hydrocarbon group of the oil-soluble film-forming corrosion inhibitor and the group adsorbed on the metal, and as a result, the imidazoline compound having a specific structure was identified. It was found that the corrosion can be suppressed very efficiently by using it, and the present invention has been accomplished.
【００１１】すなわち、本発明は、酸価が１４０〜３０
０（ｍｇＫＯＨ／ｇ）のナフテン酸と、トリエチレンテ
トラミン、テトラエチレンペンタミンおよびペンタエチ
レンヘキサミンからなる群より選ばれたアミン類の１種
以上とを反応させて得られる一般式(Ｉ)〔式中、Ｒ1、
Ｒ2はそれぞれ同一あるいは異なるナフテン酸残基を表
し、Ｒ3は−ＣＨ2ＣＨ2−、−Ｃ2Ｈ4ＮＨＣ2Ｈ4−、−
Ｃ2Ｈ4ＮＨＣ2Ｈ4ＮＨＣ2Ｈ4−を表す〕で示される分子
内に２つのイミダゾリン環を持つ化合物を有効成分とす
る油溶性皮膜性腐食防止剤。That is, the present invention has an acid value of 140 to 30.
0 (mgKOH / g) of naphthenic acid is reacted with one or more amines selected from the group consisting of triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine to obtain a compound represented by the formula (I) Medium, R 1 ,
R 2 each represent a same or different naphthenic acid residue, R 3 is -CH 2 CH 2 -, - C 2 H 4 NHC 2 H 4 -, -
C 2 H 4 NHC 2 H 4 NHC 2 H 4 −] is an oil-soluble film-forming corrosion inhibitor containing a compound having two imidazoline rings in the molecule as an active ingredient.
【００１２】[0012]
【化３】 Embedded image
【００１３】[0013]
【発明の実施の形態】以下、本発明の実施の形態を説明
する。Embodiments of the present invention will be described below.
【００１４】一般式（Ｉ）の化合物は、トリエチレンテ
トラミン、テトラエチレンペンタミンおよびペンタエチ
レンヘキサミンのうちの１種あるいは２種以上のアミン
類と酸価が１００〜３００（ｍｇＫＯＨ／ｇ）のナフテ
ン酸類を、アミン類１モルに対してナフテン酸２モルの
割合で混合し、常圧下で脱水反応によって生成した水を
溜出させながら１５０〜２００℃に加熱し相当するジア
ミド体とし、次いでさらに減圧下で水を溜出させながら
２００〜２５０℃に加熱してイミダゾリン環を形成させ
ることにより合成される。The compound of the general formula (I) comprises one or more amines selected from triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine and naphthene having an acid value of 100 to 300 (mgKOH / g). Acids are mixed at a ratio of 2 moles of naphthenic acid to 1 mole of amines and heated to 150 to 200 ° C. while distilling water generated by the dehydration reaction under normal pressure to obtain a corresponding diamide body, and then further reduced pressure. It is synthesized by heating to 200 to 250 ° C. while distilling water under the water to form an imidazoline ring.
【００１５】１分子中にイミダゾリン環が２つ入った化
合物は、公知のイミダゾリン環が１つの化合物（II）の
生成反応からその形成は類推でき、さらに反応中の溜出
してくる水の量、生成物の赤外吸収スペクトルの１６２
０ｃｍ-1付近の〔−Ｎ＝〕の存在、化学分析による３級
アミノ基の存在などでその形成が確認できる。イミダゾ
リン環化率は、全アミン価（１級、２級、３級の合計）
と３級アミン価の比から求められる。イミダゾリン環化
率は高い方が効果が高く、実際上環化率が７０％以上、
好ましくは８０％以上、さらに好ましくは９０％以上あ
れば、本発明の目的は達せられる。With respect to a compound having two imidazoline rings in one molecule, its formation can be inferred from the known reaction of producing compound (II) having one imidazoline ring, and further, the amount of water distilled out during the reaction, 162 of the infrared absorption spectrum of the product
Its formation can be confirmed by the presence of [-N =] near 0 cm -1 and the presence of a tertiary amino group by chemical analysis. Imidazoline cyclization ratio is the total amine value (total of primary, secondary and tertiary)
And the tertiary amine value ratio. The higher the imidazoline cyclization rate, the higher the effect. Actually, the cyclization rate is 70% or more,
The object of the present invention can be achieved when it is preferably 80% or more, more preferably 90% or more.
【００１６】本発明において、ナフテン酸はその酸価が
１４０〜３００(ｍｇＫＯＨ／ｇ)、好ましくは１７０〜
２６０（ｍｇＫＯＨ／ｇ）のものを用いる。この酸価の
範囲は実験の結果最適と認められたもので、酸価が１４
０(ｍｇＫＯＨ／ｇ)未満のナフテン酸は疎水性が大き過
ぎて安定な腐食防止被膜ができず、また酸価が３００
(ｍｇＫＯＨ／ｇ)を越えるナフテン酸は親水性が大き過
ぎ、炭化水素油へ溶解性が悪くなると共に水分離性も悪
くなり好ましくない。尚、本発明におけるナフテン酸酸
価は、ナフテン酸中に含まれる溶剤分を除いた実質活性
分の酸価である。In the present invention, naphthenic acid has an acid value of 140-300 (mgKOH / g), preferably 170-.
260 (mgKOH / g) is used. This acid value range was found to be optimum as a result of experiments, and the acid value was 14
Naphthenic acid of less than 0 (mgKOH / g) is too hydrophobic to form a stable corrosion preventive film, and has an acid value of 300.
Naphthenic acid exceeding (mgKOH / g) is not preferable because it is too hydrophilic and its solubility in hydrocarbon oil is poor and its water separability is poor. The acid value of naphthenic acid in the present invention is the acid value of the substantially active component excluding the solvent component contained in naphthenic acid.
【００１７】また一般式(Ｉ)において、Ｒ3は、−ＣＨ2
ＣＨ2−、−Ｃ2Ｈ4ＮＨＣ2Ｈ4−、−Ｃ2Ｈ4ＮＨＣ2Ｈ4
ＮＨＣ2Ｈ4−を表すが、−ＣＨ2ＣＨ2−が特に好まし
い。[0017] In the general formula (I), R3 is, -CH 2
CH 2 -, - C 2 H 4 NHC 2 H 4 -, - C 2 H 4 NHC 2 H 4
It represents NHC 2 H 4 —, but —CH 2 CH 2 — is particularly preferred.
【００１８】本発明の油溶性皮膜性腐食防止剤は、通
常、有機溶剤に溶解して使用される。有機溶剤として
は、一般式(Ｉ)の化合物を均一に溶解するものであれば
よく、特に限定されるものではないが、例えば、キシレ
ン、トルエン、エチルベンゼン、石油系芳香族混合溶媒
など芳香族炭化水素系溶媒、エタノール、プロパノール
等のアルコール系溶媒、メチルエチルケトン、アセトン
などのケトン系溶媒、エチレングリコールモノメチルエ
ーテル、プロピレングリコールモノメチルエーテルなど
エーテル系溶媒、その他ヂメチルスルホシシド、Ｎ−メ
チルピロリドン、γ−ブチルラクトン、ジオキサンなど
が挙げられる。一般式（Ｉ）の化合物の有機溶剤中の濃
度は、特に限定するものではないが、一般的には５〜８
０重量％である。The oil-soluble film-forming corrosion inhibitor of the present invention is usually used by dissolving it in an organic solvent. The organic solvent is not particularly limited as long as it can uniformly dissolve the compound of the general formula (I), and examples thereof include xylene, toluene, ethylbenzene, and petroleum-based aromatic mixed solvents such as aromatic carbons. Hydrogen-based solvents, alcohol-based solvents such as ethanol and propanol, ketone-based solvents such as methyl ethyl ketone and acetone, ether-based solvents such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether, and other dimethyl sulfociside, N-methylpyrrolidone, γ-butyl Examples thereof include lactone and dioxane. The concentration of the compound of general formula (I) in the organic solvent is not particularly limited, but is generally 5-8.
0% by weight.
【００１９】本発明の油溶性皮膜性腐食防止剤は、腐食
の発生している箇所の上流部に注入し、問題箇所に達す
る迄にプロセス流に十分均一に混合させることが重要で
ある。例えば、注入点の例として蒸留塔塔内循環油、蒸
留塔塔頂部のガス流体中などである。It is important that the oil-soluble film-forming corrosion inhibitor of the present invention is injected into the upstream portion of the portion where corrosion is occurring, and is mixed sufficiently uniformly in the process stream until the problem portion is reached. For example, examples of the injection point are circulating oil in the distillation column tower, in the gas fluid at the top of the distillation column, and the like.
【００２０】本発明に係る油溶性皮膜性腐食防止剤の注
入量は、腐食環境、ｐＨ、温度、装置の条件、その他そ
こを流れる炭化水素の性状などにより一律に決められる
ものではないが、一般的には対象とするプロセス中の炭
化水素に対し活性成分が０．１〜１０ｐｐｍ、好ましく
は０．３〜３ｐｐｍ、さらに好ましくは０．５〜１ｐｐ
ｍになるように注入する。注入方法は、対象とする炭化
水素流に均一に注入されればよく、特に限定するもので
はないが、注入ノズルの先が細くなっていてそこから噴
霧状に注入されるようなものが好ましく一般に使用され
ている。The injection amount of the oil-soluble film-forming corrosion inhibitor according to the present invention is not uniformly determined depending on the corrosive environment, pH, temperature, conditions of the apparatus, properties of hydrocarbons flowing therethrough, etc. Specifically, the active ingredient is 0.1 to 10 ppm, preferably 0.3 to 3 ppm, and more preferably 0.5 to 1 pp, relative to the hydrocarbon in the target process.
Inject to m. The injection method is not particularly limited as long as it is uniformly injected into the target hydrocarbon flow, but it is generally preferable that the injection nozzle has a tapered tip and is injected in a spray form. in use.
【００２１】本発明は、一般式（Ｉ）に示されるよう
に、特定のナフテン酸残基をもち、かつ分子内に２つの
イミダゾリン環を持つ化合物を有効成分とするところに
特徴がある。従来知られているこの種の化合物は、分子
内に１つのイミダゾリン環を持つ化合物であり、１つの
分子内にイミダゾリン環が増えたことの効果は、皮膜の
安定性の違いとなって現れ、同じ効果を出すためにより
少ない量で済むという利点を生むことである。The present invention is characterized in that, as shown in the general formula (I), a compound having a specific naphthenic acid residue and having two imidazoline rings in the molecule is used as an active ingredient. Conventionally known compounds of this type are compounds having one imidazoline ring in the molecule, and the effect of increasing the number of imidazoline rings in one molecule appears as a difference in the stability of the film, It has the advantage of requiring a smaller amount to produce the same effect.
【００２２】皮膜は金属表面に吸着されるが、その吸着
座はイミダゾリン環の環状窒素の不対原子にある。イミ
ダゾリン環が分子内に２つあることは、分子内に吸着座
が多くあることを意味し、１つの吸着座が脱離しても分
子全体は脱離せず、表面に固着していることである。一
方、水分離性の観点からみて、油溶性皮膜性腐食防止剤
は悪い影響を及ぼすことが懸念され、従って、腐食抑制
が満たされる添加濃度で水分離性が基準以内にあること
が要求される。本発明の油溶性皮膜性腐食防止剤は低注
入量で腐食抑制が達成されるので水分離性の上からも優
れている。The film is adsorbed on the metal surface, and its adsorption site is on the unpaired atom of the cyclic nitrogen of the imidazoline ring. The fact that there are two imidazoline rings in the molecule means that there are many adsorption sites in the molecule, and even if one adsorption site is desorbed, the entire molecule is not desorbed and is fixed on the surface. . On the other hand, from the viewpoint of water separability, it is feared that the oil-soluble film-forming corrosion inhibitor may have a bad influence, and therefore, it is required that the water separability is within the standard at the addition concentration at which the corrosion inhibition is satisfied. . The oil-soluble film-forming corrosion inhibitor of the present invention achieves corrosion inhibition with a low injection amount, and is therefore superior in terms of water separability.
【００２３】本発明の腐食防止剤は、鉄および鉄合金材
料に対して有効である。The corrosion inhibitors of the present invention are effective on iron and iron alloy materials.
【００２４】[0024]
【実施例】次に実施例によって本発明をさらに具体的に
説明する。もちろん、本発明はこれによって何ら制限さ
れるものではない。Next, the present invention will be described more specifically with reference to examples. Of course, the present invention is not limited thereby.
【００２５】〔アミン価の測定〕 全アミン価：試料約０．５ｇを精秤し、これをイソプロ
パノール５０ｍＬに溶解し、ブロムクレゾールグリーン
指示薬を２滴加え、Ｎ／１０塩酸（２−イソプロパノー
ル性）で滴定した。 ３級アミン価：試料約０．５ｇを、無水酢酸２重量部と
酢酸８重量部の混合溶液３０ｍＬに加え、９０〜１００
℃にて３０分保持した。冷却後この溶液に酢酸１０ｍＬ
を加え、クリスタルバイオレット指示薬を数滴加え、Ｎ
／１０規定過塩素酸−酢酸溶液で滴定した。[Measurement of amine value] Total amine value: About 0.5 g of a sample was precisely weighed, dissolved in 50 mL of isopropanol, 2 drops of bromcresol green indicator was added, and N / 10 hydrochloric acid (2-isopropanolic property) Titrated with. Tertiary amine value: About 0.5 g of the sample was added to 30 mL of a mixed solution of 2 parts by weight of acetic anhydride and 8 parts by weight of acetic acid, and 90 to 100
Hold at 30 ° C. for 30 minutes. 10 mL of acetic acid in this solution after cooling
, Add a few drops of crystal violet indicator, N
The titration was performed with a / 10 normal perchloric acid-acetic acid solution.
【００２６】〔本発明の腐食抑制剤〕化合物−Ａ〔一般
式(Ｉ)において、Ｒ1，Ｒ2＝酸価１７９(ｍｇＫＯＨ／
ｇ)のナフテン酸残基、Ｒ3＝−ＣＨ2ＣＨ2−の化合
物〕：酸価が１７９（ｍｇＫＯＨ／ｇ）のナフテン酸
〔大和油脂(株)製品〕とトリエチレンテトラミンをモル
比２：１の割合で混合し、窒素通気下８０℃で１時間撹
拌し、さらにこの混合物を脱水反応により分離した水を
留出しつつ１７０℃にまで昇温し、この温度で３０分
間、さらに２００℃にて２．５時間保持し、さらに減圧
下に２００℃に保持し、脱水反応を完結させるとともに
生じた水を系外に溜出させ、１分子中にイミダゾリン環
２つの化合物を得た。[Corrosion Inhibitor of the Present Invention] Compound-A [in the general formula (I), R 1 and R 2 = acid value 179 (mgKOH /
g naphthenic acid residue), R 3 = -CH 2 CH 2 - compound]: acid number 179 (mg KOH / g) of naphthenic acid [Yamato oil Corp. product] and triethylenetetramine the molar ratio of 2: The mixture was mixed in a ratio of 1 and stirred at 80 ° C. for 1 hour under aeration of nitrogen, and the mixture was heated to 170 ° C. while distilling off water separated by a dehydration reaction, and heated to 200 ° C. for 30 minutes at this temperature. The mixture was held for 2.5 hours and then at 200 ° C. under reduced pressure to complete the dehydration reaction and distill off the produced water out of the system to obtain a compound having two imidazoline rings in one molecule.
【００２７】この生成物中にはナフテン酸に含まれてい
た溶剤の一部が残っている。全アミン価は９３.５ｍｇ
ＫＯＨ／ｇ、３級アミン価は８６.２ｍｇＫＯＨ／ｇで
あり、イミダゾリン環化率は９２．２％であった。図１
にその赤外線吸収スペクトルを示す。In this product, a part of the solvent contained in naphthenic acid remains. Total amine value is 93.5mg
KOH / g, the tertiary amine value was 86.2 mgKOH / g, and the imidazoline cyclization rate was 92.2%. FIG.
Shows its infrared absorption spectrum.
【００２８】化合物−Ｂ〔一般式(Ｉ)において、Ｒ1，
Ｒ2＝酸価２０８（ｍｇＫＯＨ／ｇ）のナフテン酸残
基、Ｒ3＝−ＣＨ2ＣＨ2−の化合物〕：化合物−Ａと同
様にして、酸価が２０８（ｍｇＫＯＨ／ｇ）のナフテン
酸〔大和油脂(株)製品〕とトリエチレンテトラミンをモ
ル比２：１の割合で反応させ１分子中にイミダゾリン環
２つの化合物を得た。Compound-B [in the general formula (I), R 1 ,
R 2 = naphthoic acid residue having an acid value of 208 (mgKOH / g), R 3 = -CH 2 CH 2 -compound]: naphthenic acid having an acid value of 208 (mgKOH / g) in the same manner as for compound-A. [Product of Daiwa Yushi Co., Ltd.] and triethylenetetramine were reacted at a molar ratio of 2: 1 to obtain a compound having two imidazoline rings in one molecule.
【００２９】全アミン価は１２１.６ｍｇＫＯＨ／ｇ、
３級アミン価は１１４.４ｍｇＫＯＨ／ｇであり、イミ
ダゾリン環化率は９４．１％であった。The total amine value is 121.6 mg KOH / g,
The tertiary amine value was 114.4 mgKOH / g, and the imidazoline cyclization rate was 94.1%.
【００３０】化合物−Ｃ〔一般式(Ｉ)において、Ｒ1，
Ｒ2＝酸価２５３（ｍｇＫＯＨ／ｇ）のナフテン酸残
基、Ｒ3＝−ＣＨ2ＣＨ2−の化合物〕：化合物−Ａと同
様にして、酸価が２０８（ｍｇＫＯＨ／ｇ）のナフテン
酸〔大和油脂(株)製品〕とトリエチレンテトラミンをモ
ル比２：１の割合で反応させ１分子中にイミダゾリン環
２つの化合物を得た。Compound-C [in the general formula (I), R 1 ,
R 2 = naphthoic acid residue having an acid value of 253 (mgKOH / g), R 3 = -CH 2 CH 2 -compound]: naphthenic acid having an acid value of 208 (mgKOH / g) in the same manner as compound-A [Product of Daiwa Yushi Co., Ltd.] and triethylenetetramine were reacted at a molar ratio of 2: 1 to obtain a compound having two imidazoline rings in one molecule.
【００３１】全アミン価は１４６.８ｍｇＫＯＨ／ｇ、
３級アミン価は１３２.１ｍｇＫＯＨ／ｇであり、イミ
ダゾリン環化率は９０．０％であった。The total amine number is 146.8 mg KOH / g,
The tertiary amine value was 132.1 mgKOH / g, and the imidazoline cyclization rate was 90.0%.
【００３２】〔比較の化合物〕化合物−Ｘ〔一般式
（Ｉ）において、Ｒ4，Ｒ5＝酸価２０８（ｍｇＫＯＨ／
ｇ）のナフテン酸残基〕：化合物−Ａと同様にして、酸
価２０８（ｍｇＫＯＨ／ｇ）のナフテン酸〔大和油脂
(株)製品〕とジエチレントリアミンをモル比２：１の割
合で反応させ１分子中にイミダゾリン環１つの化合物を
得た。[Comparative Compound] Compound-X [in the general formula (I), R 4 and R 5 = acid value 208 (mgKOH /
g) naphthenic acid residue]: naphthenic acid having an acid value of 208 (mgKOH / g) [Yamato Yushi, as in Compound-A]
[Products Co., Ltd.] and diethylenetriamine were reacted at a molar ratio of 2: 1 to obtain a compound having one imidazoline ring in one molecule.
【００３３】化合物−Ｙ〔一般式(Ｉ)において、Ｒ1，
Ｒ2＝酸価１０９（ｍｇＫＯＨ／ｇ）のナフテン酸残
基、Ｒ3＝−ＣＨ2ＣＨ2−の化合物〕：化合物−Ａと同
様にして、酸価が１０９（ｍｇＫＯＨ／ｇ）のナフテン
酸〔大和油脂(株)製品〕とトリエチレンテトラミンをモ
ル比２：１の割合で反応させ１分子中にイミダゾリン環
２つの化合物を得た。Compound-Y [in the general formula (I), R 1 ,
R 2 = naphthoic acid residue having an acid value of 109 (mgKOH / g), R 3 = —CH 2 CH 2 — compound]: naphthenic acid having an acid value of 109 (mgKOH / g) in the same manner as for compound-A [Product of Daiwa Yushi Co., Ltd.] and triethylenetetramine were reacted at a molar ratio of 2: 1 to obtain a compound having two imidazoline rings in one molecule.
【００３４】化合物−Ｚ〔一般式(Ｉ)において、Ｒ1，
Ｒ2＝酸価１９３（ｍｇＫＯＨ／ｇ）のトール油脂肪酸
残基、Ｒ3＝−ＣＨ2ＣＨ2ＮＣＨ2ＣＨ2−の化合物〕：
化合物−Ａと同様にして、酸価が１９３（ｍｇＫＯＨ／
ｇ）のトール油脂肪酸〔播磨化成(株)製品〕とテトラエ
チレンペンタミンをモル比２：１の割合で反応させ１分
子中にイミダゾリン環２つの化合物を得た。Compound-Z [in the general formula (I), R 1 ,
R 2 = a tall oil fatty acid residue having an acid value of 193 (mgKOH / g), R 3 = —CH 2 CH 2 NCH 2 CH 2 — compound]:
An acid value of 193 (mgKOH /
g) tall oil fatty acid [product of Harima Kasei Co., Ltd.] and tetraethylenepentamine were reacted at a molar ratio of 2: 1 to obtain two compounds having two imidazoline rings in one molecule.
【００３５】〔腐食防止性能の評価〕腐食防止性能の評
価は図２に示す還流腐食実験装置を用いた実験によって
行った。１リットル丸底フラスコに、腐食液（トルエン
１５０ミリリットル、キシレン１５０ミリリットル、灯
油２００ミリリットル、水３０ミリリットル、濃塩酸５
ミリリットル）を入れ、テストピース（研磨、脱脂した
軟鋼３０×１５×２ｍｍ）を吊るしたソックスレー還流
器を付し、内容物を沸騰させた。還流速度を毎分２５ミ
リリットルに調整しつつ、ソックスレー還流器上部よ
り、還流量に対して所定量の本発明腐食防止剤あるいは
比較の腐食防止剤を滴下した。２時間保持した後テスト
ピースの腐食減量を測定し、腐食減量から以下の式によ
って防食率（％）を求めた。[Evaluation of Corrosion Prevention Performance] The corrosion prevention performance was evaluated by an experiment using the reflux corrosion experiment device shown in FIG. In a 1 liter round bottom flask, etchant (150 ml of toluene, 150 ml of xylene, 200 ml of kerosene, 30 ml of water, 5 ml of concentrated hydrochloric acid)
A soxhlet reflux apparatus in which a test piece (polished and degreased mild steel 30 × 15 × 2 mm) was hung was attached, and the contents were boiled. While adjusting the reflux rate to 25 ml / min, a predetermined amount of the corrosion inhibitor of the present invention or a comparative corrosion inhibitor was added dropwise from the upper portion of the Soxhlet reflux device to the reflux amount. After holding for 2 hours, the corrosion weight loss of the test piece was measured, and the corrosion protection rate (%) was calculated from the corrosion weight loss by the following formula.
【００３６】 防食率（％）＝［（Ｗｂ−Ｗａ）／（Ｗｂ）］×１００ Ｗａ：薬品添加時腐食減量（ｍｇ／ｄｍ2） Ｗｂ：薬品無添加時腐食減量（ｍｇ／ｄｍ2）Anticorrosion rate (%) = [(Wb−Wa) / (Wb)] × 100 Wa: Corrosion weight loss with chemical addition (mg / dm 2 ) Wb: Corrosion weight loss without chemical addition (mg / dm 2 ).
【００３７】〔水分離指数〕航空燃料油試験方法（ＪＩ
Ｓ Ｋ−２２７６）に基づき、マイクロセパラメーター
（Ｅｍｅｒｅｅ Ｅｌｅｃｔｒｏｎｉｃｓ，Ｉｎｃ．
製）を用いて、腐食防止剤添加時の水分離指数“ＭＳＥ
Ｐ”を測定した。 試験油として特級のイソオクタン
（１、３、５−トリメチルヘキサン）を用い、規定濃度
の防食剤を添加した後、測定を行った。[Water separation index] Aviation fuel oil test method (JI
SK-2276), based on the microseparator (Emeree Electronics, Inc.
Water separation index "MSE" when a corrosion inhibitor is added
P "was measured. Using a special grade of isooctane (1,3,5-trimethylhexane) as a test oil, a corrosion inhibitor having a specified concentration was added, and then the measurement was performed.
【００３８】この結果を表１に示す。The results are shown in Table 1.
【００３９】[0039]
【表１】 [Table 1]
【００４０】本発明の化合物−Ａ、Ｂ，Ｃは、低濃度で
防食性能に非常に優れ、かつ水分離指数も大きく良好で
ある。一方比較の化合物−Ｘは、水分離指数に優れてい
るものの腐食防止性能に劣り、化合物−Ｙ、Ｚは腐食防
止性能に優れているものの、水分離指数に劣ることがわ
かる。本発明の化合物−Ａ、Ｂ，Ｃがより高い腐食防止
効果を示すことを考えれば、低添加量で腐食防止の目的
を達成できるので、水分離指数は実質格段に向上させる
ことができることとなる。The compounds-A, B and C of the present invention are very excellent in anticorrosion performance at a low concentration and also have a large water separation index and are good. On the other hand, it can be seen that the comparative compound-X is excellent in water separation index but inferior in corrosion inhibition performance, and the compounds-Y and Z are excellent in corrosion prevention performance but inferior in water separation index. Considering that the compounds-A, B, and C of the present invention exhibit a higher corrosion inhibiting effect, the object of corrosion inhibition can be achieved with a small amount of addition, so that the water separation index can be substantially improved. .
【００４１】[0041]
【発明の効果】本発明の油溶性皮膜性腐食防止剤は、炭
化水素処理装置における金属表面の腐食防止に使用した
とき、従来の油溶性皮膜性腐食防止剤に比べて高い腐食
防止効果を示し、低添加量で充分その目的が達成出来る
ことが認められた。その結果、コスト低減に寄与できる
ばかりでなく、低添加量で腐食抑制が達成されるので水
分離性も格段に向上できる。INDUSTRIAL APPLICABILITY The oil-soluble film-forming corrosion inhibitor of the present invention shows a higher corrosion-inhibiting effect than conventional oil-soluble film-forming corrosion inhibitors when used for corrosion prevention of metal surfaces in hydrocarbon treatment equipment. It was confirmed that the objective can be sufficiently achieved with a low addition amount. As a result, not only can it contribute to cost reduction, but also corrosion inhibition can be achieved with a small amount of addition, so that water separability can be markedly improved.
【図１】 化合物−Ａの赤外線吸収スペクトル。FIG. 1 is an infrared absorption spectrum of Compound-A.
【図２】 腐食防止性能評価に用いた還流腐食実験装
置。FIG. 2 is a reflux corrosion experimental apparatus used for evaluation of corrosion prevention performance.
【符号の説明】 マントルヒーター 腐食液 テストピース ソックスレー還流器 腐食防止剤滴下 冷却器[Explanation of code] Mantle heater Corrosion liquid test piece Soxhlet reflux device Corrosion inhibitor dripping cooler
Claims (4)
ｇ）のナフテン酸と、トリエチレンテトラミン、テトラ
エチレンペンタミンおよびペンタエチレンヘキサミンか
らなる群より選ばれたアミン類の１種以上とを反応させ
て得られる一般式(Ｉ)〔式中、Ｒ1、Ｒ2はそれぞれ同一
あるいは異なるナフテン酸残基を表し、Ｒ3は−ＣＨ2Ｃ
Ｈ2−、−Ｃ2Ｈ4ＮＨＣ2Ｈ4−、−Ｃ2Ｈ4ＮＨＣ2Ｈ4Ｎ
ＨＣ2Ｈ4−を表す〕で示される分子内に２つのイミダゾ
リン環を持つ化合物を有効成分とする油溶性皮膜性腐食
防止剤。 【化１】 1. An acid value of 140 to 300 (mgKOH /
g) naphthenic acid and one or more amines selected from the group consisting of triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine, obtained by reacting the compound of the general formula (I) [wherein R 1 , R 2 each represent the same or different naphthenic acid residue, and R 3 represents —CH 2 C.
H 2 -, - C 2 H 4 NHC 2 H 4 -, - C 2 H 4 NHC 2 H 4 N
Representing HC 2 H 4 −], an oil-soluble film corrosion inhibitor containing a compound having two imidazoline rings in the molecule as an active ingredient. Embedded image
ｇ）のナフテン酸と、トリエチレンテトラミンとを反応
させて得られる一般式（Ｉ）〔式中、Ｒ1、Ｒ2はそれぞ
れ同一あるいは異なるナフテン酸残基を表し、Ｒ3は、
−ＣＨ2ＣＨ2−を表す〕で示される分子内に２つのイミ
ダゾリン環を持つ化合物を有効成分とする油溶性皮膜性
腐食防止剤。2. An acid value of 140 to 300 (mgKOH /
General formula (I) obtained by reacting naphthenic acid of g) with triethylenetetramine [wherein R 1 and R 2 represent the same or different naphthenic acid residues, and R 3 represents
Representing —CH 2 CH 2 —], an oil-soluble film corrosion inhibitor containing a compound having two imidazoline rings in the molecule as an active ingredient.
食防止剤を作用してなる炭化水素処理装置における金属
表面の腐食防止方法。3. A method for preventing corrosion of a metal surface in a hydrocarbon treatment apparatus, which comprises the oil-soluble coating corrosion inhibitor according to claim 1 or 2.
る請求項３記載の金属表面の腐食防止方法。4. The method for preventing corrosion of a metal surface according to claim 3, wherein the hydrocarbon treatment device is a crude oil atmospheric distillation column.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8051961A JP3053763B2 (en) | 1996-03-08 | 1996-03-08 | Oil soluble film corrosion inhibitor and method for preventing corrosion of metal surface using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8051961A JP3053763B2 (en) | 1996-03-08 | 1996-03-08 | Oil soluble film corrosion inhibitor and method for preventing corrosion of metal surface using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09241636A true JPH09241636A (en) | 1997-09-16 |
| JP3053763B2 JP3053763B2 (en) | 2000-06-19 |
Family
ID=12901468
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8051961A Expired - Fee Related JP3053763B2 (en) | 1996-03-08 | 1996-03-08 | Oil soluble film corrosion inhibitor and method for preventing corrosion of metal surface using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3053763B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1029000A1 (en) * | 1997-11-07 | 2000-08-23 | Henkel Corporation | Crystallization resistant amidoamine compositions |
| JP2013501126A (en) * | 2009-08-04 | 2013-01-10 | ゼネラル・エレクトリック・カンパニイ | Method for removing hydrogen sulfide from a purified hydrocarbon stream |
| WO2015100033A1 (en) * | 2013-12-27 | 2015-07-02 | Dow Global Technologies Llc | Corrosion inhibiting compositions including bis-imidazoline compounds derived from enriched linear tetramines |
| US10428454B2 (en) | 2013-12-27 | 2019-10-01 | Dow Global Technologies Llc | Textile treatment compositions including quternary bis-imidazoline compounds derived from linear tetramines useful to improve moisture management and provide antimicrobial protection |
| US10487406B2 (en) | 2013-12-27 | 2019-11-26 | Dow Global Technologies Llc | Bis-imidazoline compounds as corrosion inhibitors and preparation thereof |
-
1996
- 1996-03-08 JP JP8051961A patent/JP3053763B2/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1029000A1 (en) * | 1997-11-07 | 2000-08-23 | Henkel Corporation | Crystallization resistant amidoamine compositions |
| EP1029000A4 (en) * | 1997-11-07 | 2001-01-24 | Henkel Corp | Crystallization resistant amidoamine compositions |
| JP2013501126A (en) * | 2009-08-04 | 2013-01-10 | ゼネラル・エレクトリック・カンパニイ | Method for removing hydrogen sulfide from a purified hydrocarbon stream |
| WO2015100033A1 (en) * | 2013-12-27 | 2015-07-02 | Dow Global Technologies Llc | Corrosion inhibiting compositions including bis-imidazoline compounds derived from enriched linear tetramines |
| CN105874101A (en) * | 2013-12-27 | 2016-08-17 | 陶氏环球技术有限责任公司 | Corrosion inhibiting compositions including bis-imidazoline compounds derived from enriched linear tetramines |
| JP2017508871A (en) * | 2013-12-27 | 2017-03-30 | ダウ グローバル テクノロジーズ エルエルシー | Corrosion-inhibiting composition comprising concentrated linear tetramine-derived bisimidazoline compound |
| US10329672B2 (en) | 2013-12-27 | 2019-06-25 | Dow Global Technologies Llc | Corrosion inhibiting compositions including bis-imidazoline compounds derived from enriched linear tetramines |
| US10428454B2 (en) | 2013-12-27 | 2019-10-01 | Dow Global Technologies Llc | Textile treatment compositions including quternary bis-imidazoline compounds derived from linear tetramines useful to improve moisture management and provide antimicrobial protection |
| US10487406B2 (en) | 2013-12-27 | 2019-11-26 | Dow Global Technologies Llc | Bis-imidazoline compounds as corrosion inhibitors and preparation thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3053763B2 (en) | 2000-06-19 |
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