JPWO2018003624A1 - Composition for iron sulfide removal - Google Patents

Composition for iron sulfide removal Download PDF

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JPWO2018003624A1
JPWO2018003624A1 JP2018525091A JP2018525091A JPWO2018003624A1 JP WO2018003624 A1 JPWO2018003624 A1 JP WO2018003624A1 JP 2018525091 A JP2018525091 A JP 2018525091A JP 2018525091 A JP2018525091 A JP 2018525091A JP WO2018003624 A1 JPWO2018003624 A1 JP WO2018003624A1
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iron sulfide
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将貴 清水
将貴 清水
勇祐 齊藤
勇祐 齊藤
拓大 ▲鶴▼田
拓大 ▲鶴▼田
純市 藤
純市 藤
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Kuraray Co Ltd
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Abstract

下記一般式（１）で表されるα，β−不飽和アルデヒドを有効成分として含有する、硫化鉄除去用の組成物。（Ｒ１〜Ｒ３はそれぞれ独立して水素原子、炭素数１〜１０のアルキル基、炭素数２〜１０のアルケニル基または炭素数６〜１２のアリール基を表す。ただし、Ｒ１はＲ２またはＲ３と互いに連結して炭素数２〜６のアルキレン基を構成してもよく、Ｒ１とＲ２が同時に水素原子であることはない。）The composition for iron sulfide removal which contains the (alpha), (beta)-unsaturated aldehyde represented by following General formula (1) as an active ingredient. (R1 to R3 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, provided that R 1 is mutually exclusive with R 2 or R 3 They may be linked to form an alkylene group having 2 to 6 carbon atoms, and R1 and R2 may not simultaneously be hydrogen atoms.)

Description

本発明は、硫化鉄除去用の組成物、およびそれを用いた硫化鉄の除去方法に関する。   The present invention relates to a composition for removing iron sulfide, and a method for removing iron sulfide using the same.

天然ガス、液化天然ガス、サワーガス、原油、ナフサ、重質芳香族ナフサ、ガソリン、ケロシン、ディーゼル油、軽油、重油、ＦＣＣスラリー、アスファルト、油田濃縮物などの化石燃料や精製石油製品などの炭化水素中にしばしば存在する硫化水素は、掘削設備等に用いられる鉄を腐食して硫化鉄が発生する原因となる。硫化鉄は化石燃料や精製石油製品の製造設備内に堆積物として蓄積し、熱交換器、冷却塔、反応容器、輸送パイプラインまたは炉などの機器類の操作効率の低下や設備保全のための正確な測定の妨げとなるため、これを除去することが望まれる。   Natural gas, liquefied natural gas, sour gas, crude oil, naphtha, heavy aromatic naphtha, gasoline, kerosene, diesel oil, diesel oil, light oil, heavy oil, FCC slurry, asphalt, hydrocarbons such as asphalt, oil field concentrates and refined petroleum products Hydrogen sulfide, which is often present in the inside, corrodes iron used in drilling facilities and the like to cause iron sulfide to be generated. Iron sulfide accumulates as deposits in facilities for producing fossil fuels and refined petroleum products, and reduces the operation efficiency of equipment such as heat exchangers, cooling towers, reaction vessels, transport pipelines or furnaces, and for facility maintenance. It is desirable to remove it as it interferes with accurate measurement.

硫化鉄を除去する方法として、アクロレインを用いて硫化鉄を溶解する方法が知られており、２０１１年１０月３０日〜１１月２日に米国コロラド州デンバーで開かれたSPE Annual Technical Conference and Exhibition SPE 146080でも、アクロレインを有効成分とする硫化鉄除去に関して発表されている。しかしながら、アクロレインは毒性が強く、労働安全上および環境安全上で厳しくその濃度が規制されている化合物であり、取り扱いに注意を要するという問題がある。加えて、アクロレインは極めて重合しやすく、熱安定性に欠けるという点や、ｐＨ安定性に欠け、使用される環境のｐＨによっては徐々に存在量が減少してしまう点も取り扱う上で問題となる。   As a method of removing iron sulfide, a method of dissolving iron sulfide using acrolein is known, and SPE Annual Technical Conference and Exhibition held in Denver, Colorado, USA from October 30 to November 2, 2011. SPE 146080 also describes iron sulfide removal using acrolein as an active ingredient. However, acrolein is a highly toxic compound whose concentration is strictly regulated in terms of occupational safety and environmental safety, and there is a problem that it requires careful handling. In addition, acrolein is very easy to polymerize and lacks thermal stability, and it also has problems in handling pH stability and the fact that its amount may decrease gradually depending on the pH of the environment used. .

SPE Annual Technical Conference and Exhibition SPE 146080, 2011年; http://dx.doi.org/10.2118/146080-MSSPE Annual Technical Conference and Exhibition SPE 146080, 2011; http://dx.doi.org/10.2118/146080-MS

上記のように、硫化鉄の除去を目的としてアクロレインを用いるには、安全性や熱安定性、およびｐＨ安定性の面において問題点があり、より安全で安定な化合物による代替が望まれている。しかして、本発明の目的は、熱安定性およびｐＨ安定性の高い有効成分を有し、かつ、硫化鉄を安全に効率よく除去できる組成物を提供することにある。   As mentioned above, there is a problem in terms of safety, thermal stability and pH stability to use acrolein for the purpose of removing iron sulfide, and substitution with a safer and stable compound is desired . Therefore, an object of the present invention is to provide a composition having an active ingredient having high thermal stability and pH stability and capable of safely and efficiently removing iron sulfide.

本発明によれば、上記した目的は、下記［１］〜［７］により達成される。
［１］下記一般式（１）で表されるα，β−不飽和アルデヒド（以下、アルデヒド（１）と称する）を有効成分として含有する、硫化鉄除去用の組成物。According to the present invention, the above-mentioned object is achieved by the following [1] to [7].
[1] A composition for removing iron sulfide, which contains an α, β-unsaturated aldehyde (hereinafter referred to as aldehyde (1)) represented by the following general formula (1) as an active ingredient.

Figure 2018003624
Figure 2018003624

（Ｒ１〜Ｒ３はそれぞれ独立して水素原子、炭素数１〜１０のアルキル基、炭素数２〜１０のアルケニル基または炭素数６〜１２のアリール基を表す。ただし、Ｒ１はＲ２またはＲ３と互いに連結して炭素数２〜６のアルキレン基を構成してもよく、Ｒ１とＲ２が同時に水素原子であることはない。）
［２］Ｒ１〜Ｒ３がそれぞれ独立して水素原子または炭素数１〜５のアルキル基である、［１］の組成物。
［３］Ｒ３が水素原子である、［１］または［２］の組成物。
［４］［１］〜［３］のいずれかの組成物を硫化鉄に接触させることを特徴とする、硫化鉄の除去方法。
［５］前記組成物中のアルデヒド（１）を、硫化鉄１質量部に対し０．１〜１００質量部となるように添加する、［４］の方法。
［６］前記組成物中のアルデヒド（１）と硫化鉄を−３０℃〜１５０℃の範囲で接触させることを特徴とする、［４］または［５］の方法。
［７］硫化鉄を除去するための、［１］〜［３］のいずれかの組成物の使用。(R 1 to R 3 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, provided that R 1 is R 2 Or R 3 may be linked to each other to form an alkylene group having 2 to 6 carbon atoms, and R 1 and R 2 may not simultaneously be a hydrogen atom.)
[2] The composition of [1], wherein each of R 1 to R 3 independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
[3] The composition of [1] or [2], wherein R 3 is a hydrogen atom.
[4] A method for removing iron sulfide, comprising bringing iron sulfide into contact with the composition according to any one of [1] to [3].
[5] The method of [4], wherein the aldehyde (1) in the composition is added in an amount of 0.1 to 100 parts by mass with respect to 1 part by mass of iron sulfide.
[6] The method according to [4] or [5], wherein the aldehyde (1) in the composition and iron sulfide are brought into contact in the range of -30 ° C to 150 ° C.
[7] Use of the composition according to any one of [1] to [3] for removing iron sulfide.

本発明の組成物はアルデヒド（１）を含有することで、硫化鉄の除去性能に優れる。
特に、アクロレインを含有する従来の硫化鉄除去剤に比べ、本発明の組成物は毒性が極めて低く、熱安定性およびｐＨ安定性が高いという利点を有する。この理由は必ずしも明らかではないが、アルデヒド（１）はβ位に少なくとも１つのアルキル基、アルケニル基またはアリール基を有するため、β位に置換基を有しないアクロレインと比較し、生体分子や生長鎖などの嵩高い分子のβ位への付加反応が起こりにくいことが要因のひとつと考えられる。一方で、硫化鉄の除去に関しては、硫化鉄と平衡状態にある硫化水素と結合し、これを除去することで硫化鉄の溶解が促進され、結果的に硫化鉄が除去されると考えられるが、β位に置換基を有していても、一般的に小さい分子である硫化水素からの攻撃はさほど阻害されず、硫化鉄除去性能が保たれるものと考えられる。The composition of the present invention is excellent in the iron sulfide removal performance by containing the aldehyde (1).
In particular, the composition of the present invention has the advantages of extremely low toxicity, high thermal stability and high pH stability, as compared to conventional iron sulfide removers containing acrolein. Although this reason is not necessarily clear, since aldehyde (1) has at least one alkyl group, alkenyl group or aryl group at the β position, it is a biomolecule or a long chain as compared with acrolein having no substituent at the β position. It is considered that one of the factors is that the addition reaction of bulky molecules to the β-position is unlikely to occur. On the other hand, with regard to the removal of iron sulfide, it is thought that the dissolution of iron sulfide is promoted by binding to hydrogen sulfide in equilibrium with iron sulfide and the removal thereof results in the removal of iron sulfide as a result. Even if it has a substituent at the β position, it is considered that the attack from hydrogen sulfide, which is a generally small molecule, is not significantly inhibited and iron sulfide removal performance is maintained.

セネシオアルデヒド（ＳＡＬ）のｐＨ安定性を示すグラフである。It is a graph which shows pH stability of a senesio aldehyde (SAL). アクロレインのｐＨ安定性を示すグラフである。It is a graph which shows the pH stability of acrolein.

本発明の組成物は有効成分としてアルデヒド（１）を含有することを特徴とする。
アルデヒド（１）においてＲ１〜Ｒ３がそれぞれ独立して表す炭素数１〜１０のアルキル基は直鎖状でも分岐状でも環状でもよく、例えばメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基、ｎ−オクチル基、ｎ−デシル基、ｎ−ドデシル基、シクロペンチル基などが挙げられる。硫化鉄の除去性能の観点から、中でもメチル基、エチル基またはｎ−プロピル基が好ましく、メチル基またはエチル基がより好ましく、メチル基がさらに好ましい。
Ｒ１〜Ｒ３がそれぞれ独立して表す炭素数２〜１０のアルケニル基は直鎖状でも分岐状でも環状でもよく、例えばビニル基、アリル基、１−ペンテン−１−イル基、４−メチル−３−ペンテン−１−イル基、４−ペンテン−１−イル基、１−ヘキセン−１−イル基、１−オクテン−１−イル基、１−デセン−１−イル基などが挙げられる。中でも炭素数１〜８のアルケニル基が好ましく、炭素数１〜６のアルケニル基がより好ましい。
Ｒ１〜Ｒ３がそれぞれ独立して表す炭素数６〜１２のアリール基は、例えばフェニル基、トリル基、エチルフェニル基、キシリル基、トリメチルフェニル基、ナフチル基、ビフェニリル基などが挙げられる。中でも炭素数６〜１０のアリール基が好ましい。
また、Ｒ１がＲ２またはＲ３と互いに連結して炭素数２〜６のアルキレン基を表す場合、当該アルキレン基としては例えばエチレン基、ｎ−プロピレン基、ｎ−ブチレン基、ｎ−ペンチレン基、ｎ−へキシレン基、２−メチルエチレン基、１，２−ジメチルエチレン基、２−メチル−ｎ−プロピレン基、２，２−ジメチル−ｎ−プロピレン基、３−メチル−ｎ−ペンチレン基などが挙げられる。
Ｒ１〜Ｒ３はそれぞれ独立して水素原子または炭素数１〜５のアルキル基であることが好ましい。
硫化鉄の除去性能を有し、かつ熱安定性およびｐＨ安定性を確保する観点から、Ｒ１、Ｒ２の少なくとも一方がメチル基であることが好ましく、Ｒ１、Ｒ２が共にメチル基であることがより好ましい。
また硫化水素との反応を促進し、硫化鉄を効率よく除去する観点からは、Ｒ３は水素原子であることが好ましい。The composition of the present invention is characterized by containing an aldehyde (1) as an active ingredient.
The alkyl group having 1 to 10 carbon atoms represented by R 1 to R 3 independently in aldehyde (1) may be linear, branched or cyclic, and examples thereof include a methyl group, an ethyl group, an n-propyl group and an isopropyl group. And n-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, cyclopentyl group and the like. Among them, a methyl group, an ethyl group or an n-propyl group is preferable, a methyl group or an ethyl group is more preferable, and a methyl group is further preferable from the viewpoint of the removal performance of iron sulfide.
The alkenyl group having 2 to 10 carbon atoms which R 1 to R 3 independently represent may be linear, branched or cyclic, and examples thereof include a vinyl group, an allyl group, a 1-penten-1-yl group, and 4-methyl. -3-penten-1-yl group, 4-penten-1-yl group, 1-hexen-1-yl group, 1-octen-1-yl group, 1-decene-1-yl group, etc. may be mentioned. Especially, a C1-C8 alkenyl group is preferable and a C1-C6 alkenyl group is more preferable.
Examples of the aryl group having 6 to 12 carbon atoms represented by R 1 to R 3 independently include phenyl group, tolyl group, ethylphenyl group, xylyl group, trimethylphenyl group, naphthyl group, biphenylyl group and the like. Among them, aryl groups having 6 to 10 carbon atoms are preferable.
Moreover, when R 1 mutually connects with R 2 or R 3 to represent an alkylene group having 2 to 6 carbon atoms, examples of the alkylene group include ethylene group, n-propylene group, n-butylene group and n-pentylene group , N-hexylene group, 2-methylethylene group, 1,2-dimethylethylene group, 2-methyl-n-propylene group, 2,2-dimethyl-n-propylene group, 3-methyl-n-pentylene group, etc. Can be mentioned.
It is preferable that R < 1 > -R < 3 > is respectively independently a hydrogen atom or a C1-C5 alkyl group.
It is preferable that at least one of R 1 and R 2 is a methyl group from the viewpoint of having iron sulfide removal performance and securing thermal stability and pH stability, and both R 1 and R 2 are methyl groups. It is more preferable that
Further, from the viewpoint of promoting the reaction with hydrogen sulfide and efficiently removing iron sulfide, R 3 is preferably a hydrogen atom.

アルデヒド（１）としては、例えば２−ブテナール、２−ペンテナール、２−ヘキセナール、２−ヘプテナール、２−オクテナール、２−ノネナール、２−デセナール、２−ウンデセナール、２−ドデセナール、２−トリデセナール、４−メチル−２−ペンテナール、４−メチル−２−ヘキセナール、５−メチル−２−ヘキセナール、４，４−ジメチル−２−ペンテナール、６−メチル−２−ヘプテナール、４−エチル−２−ヘキセナール、２−メチル−２−ブテナール、２−メチル−２−ペンテナール、２−メチル−２−ヘキセナール、２−メチル−２−ヘプテナール、２−メチル−２−オクテナール、４−メチル−２−プロピル−２−ヘキセナール、２，４−ジメチル−２−ペンテナール、２，４−ジメチル−２−ヘキセナール、２，４−ジメチル−２−ヘプテナール、２，５−ジメチル−２−ヘキセナール、２，６−ジメチル−２−ヘプテナール、２，４，４−トリメチル−２−ペンテナール、２−エチル−２−ブテナール、２−エチル−２−ペンテナール、２−エチル−２−ヘキセナール、２−エチル−２−ヘプテナール、２−エチル−２−オクテナール、２−エチル−４−メチル−２−ペンテナール、２−エチル−４−メチル−２−ヘキセナール、２−プロピル−２−ブテナール、２−プロピル−２−ペンテナール、２−プロピル−２−ヘキセナール、２−プロピル−２−ヘプテナール、２−プロピル−４−メチル−２−ペンテナール、２−プロピル−５−メチル−２−ヘキセナール、２−イソプロピル−２−ブテナール、２−イソプロピル−４−メチル−２−ペンテナール、２−イソプロピル−４−メチル−２−ヘキセナール、２−イソプロピル−５−メチル−２−ヘキセナール、２−ブチル−２−ブテナール、２−ブチル−２−ペンテナール、２−ブチル−２−ヘキセナール、２−ブチル−２−ヘプテナール、２−ブチル−２−オクテナール、２−イソブチル−２−ヘプテナール、２−イソブチル−６−メチル−２−ヘプテナール、２−ペンチル−２−ブテナール、２−ペンチル−２−ペンテナール、２−ペンチル−２−ヘキセナール、２−ペンチル−２−ヘプテナール、２−ペンチル−２−オクテナール、３−メチル−２−ブテナール、３−メチル−２−ペンテナール、３−メチル−２−ヘキセナール、３−メチル−２−ヘプテナール、３−メチル−２−オクテナール、３−メチル−２−ノネナール、３−メチル−２−デセナール、３−メチル−２−ウンデセナール、３−メチル−２−ドデセナール、３−メチル−２−トリデセナール、３−エチル−２−ペンテナール、３，４−ジメチル−２−ペンテナール、３，４，４−トリメチル−２−ペンテナール、３−イソプロピル−４−メチル−２−ペンテナール、３−エチル−２−ヘキセナール、３−プロピル−２−ヘキセナール、３，５−ジメチル−２−ヘキセナール、３−（ｔ−ブチル）−４，４−ジメチル−２−ペンテナール、３−ブチル−２−ヘプテナール、２，３−ジメチル−２−ブテナール、２−エチル−３−メチル−２−ブテナール、２−イソプロピル−３−メチル−２−ブテナール、２，３−ジメチル−２−ペンテナール、２，３，４−トリメチル−２−ヘキセナール、２−イソブチル−３−メチル−２−ブテナール、３−メチル−２−ペンチル−２−ペンテナール、２，３−ジエチル−２−へプテナール、２−（１，１−ジメチルプロピル）−３−メチル−２−ブテナール、３，５，５−トリメチル−２−ヘキセナール、２，３，４−トリメチル−２−ペンテナール、２−シクロプロピリデンプロパナール、２−シクロペンチリデンプロパナール、２−シクロペンチリデンヘキサナール、２−（３−メチルシクロペンチリデン）プロパナール、２−シクロヘキシリデンプロパナール、２−（２−メチルシクロヘキシリデン）プロパナール、２−シクロヘキシリデンブタナール、２−シクロヘキシリデンヘキサナール、１−ホルミルシクロブテン、１−ホルミル−３，３−ジメチルシクロブテン、１−シクロプロピル−２−ホルミルシクロブテン、１−ホルミルシクロペンテン、５−エチル−１−ホルミルシクロペンテン、１−ホルミル−３−メチルシクロペンテン、１−ホルミル−４−メチルシクロペンテン、１−ホルミル−５−メチルシクロペンテン、１−ホルミル−３，３−ジメチルシクロペンテン、１−ホルミル−４，５−ジメチルシクロペンテン、１−ホルミル−２−メチルシクロペンテン、１−ホルミル−５−イソプロル−２−メチルシクロペンテン、１−ホルミル−２，５，５−トリメチルシクロペンテン、１−ホルミルシクロヘキセン、１−ホルミル−３−メチルシクロヘキセン、１−ホルミル−４−メチルシクロヘキセン、１−ホルミル−５−メチルシクロヘキセン、１−ホルミル−６−メチルシクロヘキセン、１−ホルミル−３，３−ジメチルシクロヘキセン、１−ホルミル−５，５−ジメチルシクロヘキセン、１−ホルミル−２メチルシクロヘキセン、１−ホルミル−２，５，６，６−テトラメチルシクロヘキセン、１−ホルミル−２，４，６，６−テトラメチルシクロヘキセン、１−ホルミルシクロヘプテン、１−ホルミル−２−メチルシクロヘプテン、１−ホルミル−３−メチルシクロヘプテン、１−ホルミルシクロオクテン、２，４−ペンタジエナール、２，４−ヘキサジエナール、２，５−ヘキサジエナール、５−メチル−２，４−ヘキサジエナール、２，４−ヘプタジエナール、２，４−オクタジエナール、２，７−オクタジエナール、３，７−ジメチル−２，６−オクタジエナール（シトラール）、２，４，６−オクタトリエナール、７−メチル−２，４，６−オクタトリエナール、２，４−ノナジエナール、２，６−ノナジエナール、４，８−ジメチル−２，７−ノナジエナール、２，４−デカジエナール、２，４−ウンデカジエナール、２，４−ドデカジエナール、２，４−トリデカジエナール、２，４，７−トリデカトリエナール、３−フェニルプロペナール、３−フェニル−２−メチルプロペナール、３−（ｏ−トリル）プロペナール、３−（ｐ−トリル）プロペナール、３−ナフチルプロペナールなどが挙げられる。中でも、３−メチル−２−ブテナール、３−メチル−２−ペンテナール、３−メチル−２−ヘキセナール、３−メチル−２−ヘプテナール、３−メチル−２−オクテナール、３，７−ジメチル−２，６−オクタジエナール（シトラール）、３−エチル−２−ペンテナール、３−エチル−２−ヘキセナール、３−プロピル−２−ヘキセナールが好ましく、３−メチル−２−ブテナール、３−メチル−２−ペンテナール、３−エチル−２−ペンテナールがより好ましく、３−メチル−２−ブテナール（セネシオアルデヒド、以下単にＳＡＬと称する）がさらに好ましい。
なお、ｔｒａｎｓ体およびｃｉｓ体を有する化合物については、いずれか一方を用いてもよいし、混合物を用いてもよい。混合物を用いる場合、任意の混合比のものを用いることができる。Examples of the aldehyde (1) include 2-butenal, 2-pentenal, 2-hexenal, 2-heptenal, 2-octenal, 2-nonenal, 2-decenal, 2-undecenal, 2-dodecenal, 2-tridecenal, 4- Methyl-2-pentenal, 4-methyl-2-hexenal, 5-methyl-2-hexenal, 4,4-dimethyl-2-pentenal, 6-methyl-2-heptenal, 4-ethyl-2-hexenal, 2- Methyl-2-butenal, 2-methyl-2-pentenal, 2-methyl-2-hexenal, 2-methyl-2-heptenal, 2-methyl-2-octenal, 4-methyl-2-propyl-2-hexenal, 2,4-dimethyl-2-pentenal, 2,4-dimethyl-2-hexenal, 2,4 Dimethyl-2-heptenal, 2,5-dimethyl-2-hexenal, 2,6-dimethyl-2-heptenal, 2,4,4-trimethyl-2-pentenal, 2-ethyl-2-butenal, 2-ethyl-butenal 2-pentenal, 2-ethyl-2-hexenal, 2-ethyl-2-heptenal, 2-ethyl-2-octenal, 2-ethyl-4-methyl-2-pentenal, 2-ethyl-4-methyl-2- Hexenal, 2-propyl-2-butenal, 2-propyl-2-pentenal, 2-propyl-2-hexenal, 2-propyl-2-heptenal, 2-propyl-4-methyl-2-pentenal, 2-propyl- 5-Methyl-2-hexenal, 2-isopropyl-2-butenal, 2-isopropyl-4-methyl-2-pentena , 2-isopropyl-4-methyl-2-hexenal, 2-isopropyl-5-methyl-2-hexenal, 2-butyl-2-butenal, 2-butyl-2-pentenal, 2-butyl-2-hexenal, 2-Butyl-2-heptenal, 2-Butyl-2-octenal, 2-isobutyl-2-heptenal, 2-isobutyl-6-methyl-2-heptenal, 2-pentyl-2-butenal, 2-pentyl-2- Pentenal, 2-pentyl-2-hexenal, 2-pentyl-2-heptenal, 2-pentyl-2-octenal, 3-methyl-2-butenal, 3-methyl-2-pentenal, 3-methyl-2-hexenal, 3-methyl-2-heptenal, 3-methyl-2-octenal, 3-methyl-2-nonenal, 3- Methyl-2-decenal, 3-methyl-2-undecenal, 3-methyl-2-dodecenal, 3-methyl-2-tridecenal, 3-ethyl-2-pentenal, 3,4-dimethyl-2-pentenal, 3, 4,4-trimethyl-2-pentenal, 3-isopropyl-4-methyl-2-pentenal, 3-ethyl-2-hexenal, 3-propyl-2-hexenal, 3,5-dimethyl-2-hexenal, 3- (T-butyl) -4,4-dimethyl-2-pentenal, 3-butyl-2-heptenal, 2,3-dimethyl-2-butenal, 2-ethyl-3-methyl-2-butenal, 2-isopropyl- 3-Methyl-2-butenal, 2,3-dimethyl-2-pentenal, 2,3,4-trimethyl-2-hexenal, 2-isob Ru-3-methyl-2-butenal, 3-methyl-2-pentyl-2-pentenal, 2,3-diethyl-2-heptenal, 2- (1,1-dimethylpropyl) -3-methyl-2- Butenal, 3,5,5-trimethyl-2-hexenal, 2,3,4-trimethyl-2-pentenal, 2-cyclopropylidenepropanal, 2-cyclopentylidenepropanal, 2-cyclopentylidenehexanal, 2 -(3-Methylcyclopentylidene) propanal, 2-cyclohexylidenepropanal, 2- (2-methylcyclohexylidene) propanal, 2-cyclohexylidenebutanal, 2-cyclohexylidenehexanal, 1- Formylcyclobutene, 1-formyl-3,3-dimethylcyclobutene, 1-cyclopropyl-2 Formylcyclobutene, 1-formylcyclopentene, 5-ethyl-1-formylcyclopentene, 1-formyl-3-methylcyclopentene, 1-formyl-4-methylcyclopentene, 1-formyl-5-methylcyclopentene, 1-formyl-3 , 3-Dimethylcyclopentene, 1-formyl-4,5-dimethylcyclopentene, 1-formyl-2-methylcyclopentene, 1-formyl-5-isoproyl-2-methylcyclopentene, 1-formyl-2,5,5-trimethyl Cyclopentene, 1-formylcyclohexene, 1-formyl-3-methylcyclohexene, 1-formyl-4-methylcyclohexene, 1-formyl-5-methylcyclohexene, 1-formyl-6-methylcyclohexene, 1-formyl-3, 3 -Dimeth 1-formyl-5,5-dimethylcyclohexene, 1-formyl-2 methylcyclohexene, 1-formyl-2,5,6,6-tetramethylcyclohexene, 1-formyl-2,4,6,6- Tetramethylcyclohexene, 1-formylcycloheptene, 1-formyl-2-methylcycloheptene, 1-formyl-3-methylcycloheptene, 1-formylcyclooctene, 2,4-pentadienal, 2,4 Hexadienal, 2,5-hexadienal, 5-methyl-2,4-hexadienal, 2,4-heptadienal, 2,4-octadienal, 2,7-octadienal, 3,7 -Dimethyl-2,6-octadienal (citral), 2,4,6-octatrienal, 7-methyl-2,4,6-ok Trienal, 2,4-nonadienal, 2,6-nonadienal, 4,8-dimethyl-2,7-nonadienal, 2,4-decadienal, 2,4-undecadienal, 2,4-dodecadienal, 2,4 -Tridecadienal, 2,4,7-tridecatrienal, 3-phenylpropenal, 3-phenyl-2-methylpropenal, 3- (o-tolyl) propenal, 3- (p-tolyl) propenal, 3-naphthylpropenal and the like. Among them, 3-methyl-2-butenal, 3-methyl-2-pentenal, 3-methyl-2-hexenal, 3-methyl-2-heptenal, 3-methyl-2-octenal, 3, 7-dimethyl-2, 6-octadienal (citral), 3-ethyl-2-pentenal, 3-ethyl-2-hexenal, 3-propyl-2-hexenal is preferable, 3-methyl-2-butenal, 3-methyl-2-pentenal 3-ethyl-2-pentenal is more preferable, and 3-methyl-2-butenal (senecioaldehyde, hereinafter simply referred to as SAL) is more preferable.
In addition, about the compound which has trans body and cis body, any one may be used and a mixture may be used. When using a mixture, the thing of arbitrary mixing ratios can be used.

アルデヒド（１）は市販品を用いてもよいし、対応するα，β−不飽和アルコールの酸化脱水素反応によって合成してもよい（例えば特開昭６０−２２４６５２号公報参照）。   Aldehyde (1) may be a commercially available product or may be synthesized by the oxidative dehydrogenation reaction of the corresponding α, β-unsaturated alcohol (see, for example, JP-A-60-224652).

本発明の組成物における有効成分であるアルデヒド（１）の含有割合は、使用態様に応じて適宜設定することができるが、通常１〜９９．９質量％であり、費用対効果の観点から、好ましくは５〜９９．９質量％であり、より好ましくは５〜９５質量％である。   Although the content rate of the aldehyde (1) which is an active ingredient in the composition of this invention can be suitably set according to a use aspect, it is 1 to 99.9 mass% normally, and it is a cost-effective viewpoint. Preferably it is 5-99.9 mass%, More preferably, it is 5-95 mass%.

本発明の組成物は、アクロレイン、テトラキス（ヒドロキシメチル）ホスフィンまたは対応するホスホニウム塩、塩酸、ギ酸などの、他の硫化鉄除去剤を本発明の効果を損なわない範囲において含有していてもよい。
また、本発明の組成物はシクロヘキサン、トルエン、キシレン、重質芳香族ナフサ、石油蒸留物；メタノール、エタノール、エチレングリコールなどの炭素数１〜１０のモノアルコールまたはジオール；などの適当な溶媒を含有していてもよい。The composition of the present invention may contain other iron sulfide removing agents such as acrolein, tetrakis (hydroxymethyl) phosphine or corresponding phosphonium salts, hydrochloric acid, formic acid and the like within the range that does not impair the effect of the present invention.
In addition, the composition of the present invention contains a suitable solvent such as cyclohexane, toluene, xylene, heavy aromatic naphtha, petroleum distillate; C 1-10 monoalcohol or diol such as methanol, ethanol, ethylene glycol, etc. It may be done.

本発明の組成物は、アルデヒド（１）以外に、本発明の効果を損なわない限り、界面活性剤、腐食防止剤、脱酸素剤、鉄分制御剤、架橋剤、ブレーカー、凝集剤、温度安定剤、ｐＨ調整剤、脱水調整剤、膨潤防止剤、スケール防止剤、殺生物剤、摩擦低減剤、消泡剤、逸泥防止剤、潤滑剤、粘土分散剤、加重剤、ゲル化剤などの成分を含有していてもよい。   The composition of the present invention is, besides the aldehyde (1), a surfactant, a corrosion inhibitor, an oxygen scavenger, an iron control agent, a crosslinking agent, a breaker, a coagulant, a temperature stabilizer, as long as the effects of the present invention are not impaired. , PH adjusters, dehydration adjusters, anti-swelling agents, scale inhibitors, biocides, friction reducers, antifoam agents, anti-smud agents, lubricants, clay dispersants, weighting agents, gelling agents, etc. May be contained.

本発明の組成物の製造方法は特に限定されず、例えばアルデヒド（１）に、前記他の硫化鉄除去剤や溶媒などの任意成分を添加し混合することなどによって製造できる。
本発明の組成物は好適には液状であるが、硫化鉄を除去するために使用する形態に応じて、適宜担体などに担持させ、粉体、流体などの固体状としてもよい。The method for producing the composition of the present invention is not particularly limited. For example, it can be produced by adding and mixing optional components such as the above-mentioned other iron sulfide removing agent and solvent to the aldehyde (1).
The composition of the present invention is preferably in the form of liquid, but it may be supported on a carrier or the like as appropriate depending on the form used for removing iron sulfide, and may be in the form of solid such as powder or fluid.

本発明の好ましい実施態様の例としては、硫化鉄の除去に十分な量の本発明の組成物を、硫化鉄を含む液体へ添加して処理を行う。本発明の組成物を用いての、硫化鉄を除去する方法においては、本発明の組成物中に含まれるアルデヒド（１）の量が、硫化鉄１質量部に対して好ましくは０．１〜１００質量部、より好ましくは２〜１００質量部となるよう添加する。本発明の組成物を、硫化鉄を含む液体に添加して接触させ、処理を行う際の温度は好ましくは０℃〜１５０℃、より好ましくは２０℃〜１３０℃の範囲である。   As an example of a preferred embodiment of the present invention, the treatment is carried out by adding an amount of the composition of the present invention sufficient to remove iron sulfide to a liquid containing iron sulfide. In the method of removing iron sulfide using the composition of the present invention, the amount of aldehyde (1) contained in the composition of the present invention is preferably 0.1 to 1 part by mass of iron sulfide. 100 parts by mass, more preferably 2 to 100 parts by mass. The composition of the present invention is added to a liquid containing iron sulfide and brought into contact, and the temperature at which the treatment is carried out is preferably in the range of 0 ° C to 150 ° C, more preferably 20 ° C to 130 ° C.

以下、実施例等により本発明を具体的に説明するが、本発明は以下の例により何ら限定されない。なお、実施例および比較例で用いたＳＡＬ、シトラールおよびアクロレインは以下のものである。
ＳＡＬ：特開昭６０−２２４６５２号公報に記載の方法に準じ、プレノールから合成したもの（純度９８．１％）
シトラール：株式会社クラレ製（純度９８．０％、ｔｒａｎｓ：ｃｉｓ＝５１：４９〜５７：４３（モル比））
アクロレイン：東京化成工業株式会社製、安定剤としてヒドロキノン含有Hereinafter, the present invention will be specifically described by way of examples and the like, but the present invention is not limited at all by the following examples. The SAL, citral and acrolein used in Examples and Comparative Examples are as follows.
SAL: synthesized from prenol according to the method described in JP-A 60-224652 (purity 98.1%)
Citral: Kuraray Co., Ltd. (purity 98.0%, trans: cis = 51: 49 to 57: 43 (molar ratio))
Acrolein: made by Tokyo Chemical Industry Co., Ltd., containing hydroquinone as a stabilizer

＜実施例１＞硫化鉄除去試験（ＳＡＬ）
温度計、攪拌機、冷却管を備えた１Ｌの三口フラスコに蒸留水を５００ｍＬ、１ｍｏｌ／Ｌ塩酸を１ｍＬ、硫化ナトリウム・９水和物を１２０．０ｍｇ（０．５ｍｍｏｌ）、硫酸鉄・７水和物を１３８．２（０．５ｍｍｏｌ）加え、攪拌したところ硫化鉄が微細な黒色沈殿として生成した。そこにＳＡＬを１２６．３ｍｇ（１．５ｍｍｏｌ）添加し、反応液を５００ｒｐｍで攪拌しながら５０℃に昇温した。ＳＡＬを添加した時点を０時間とし、硫化鉄の様子を観察した結果、４時間後には硫化鉄は溶解し、反応液は無色透明になった。<Example 1> Iron sulfide removal test (SAL)
In a 1 L three-necked flask equipped with a thermometer, a stirrer and a condenser, 500 mL of distilled water, 1 mL of 1 mol / L hydrochloric acid, 120.0 mg (0.5 mmol) of sodium sulfide 9 hydrate, iron sulfate 7 hydration The substance was added 138.2 (0.5 mmol) and stirred to form iron sulfide as a fine black precipitate. 126.3 mg (1.5 mmol) of SAL was added there, and the reaction liquid was heated up to 50 degreeC, stirring at 500 rpm. The point of time when the SAL was added was 0 hour, and the state of iron sulfide was observed. As a result, after 4 hours, the iron sulfide was dissolved, and the reaction solution became colorless and transparent.

＜実施例２＞硫化鉄除去試験（シトラール）
ＳＡＬに代えてシトラールを用いた以外は実施例１と同様の試験を実施した。７時間後には硫化鉄は溶解し、反応液は無色透明になった。<Example 2> Iron sulfide removal test (Citral)
The same test as in Example 1 was performed except that citral was used instead of SAL. After 7 hours, the iron sulfide dissolved and the reaction solution became colorless and transparent.

＜比較例１＞硫化鉄除去試験（アクロレイン）
ＳＡＬに代えてアクロレインを用いた以外は実施例１と同様の試験を実施した。４時間後には硫化鉄は溶解し、反応液は無色透明になった。Comparative Example 1 Iron Sulfide Removal Test (Acrolein)
The same test as in Example 1 was conducted except that acrolein was used instead of SAL. After 4 hours, the iron sulfide dissolved and the reaction solution became colorless and transparent.

＜試験例１＞熱安定性試験
ＳＡＬおよびアクロレインをそれぞれ５０ｍＬ三口フラスコに入れ、窒素雰囲気下で５０℃に昇温し、昇温直後のＳＡＬおよびアクロレインの含有量を１００％とした際の含有率の変化を、内部標準を用いたガスクロマトグラフィーによる検量線法で観察した。結果を表１に示す。<Test Example 1> Thermal stability test Each of SAL and acrolein was placed in a 50 mL three-necked flask, and the temperature was raised to 50 ° C. under a nitrogen atmosphere, and the content when making SAL and acrolein content 100% immediately after heating. The change of was observed by a calibration curve method by gas chromatography using an internal standard. The results are shown in Table 1.

［ガスクロマトグラフィー分析］
分析機器：ＧＣ−１４Ａ（株式会社島津製作所製）
検出器：ＦＩＤ（水素炎イオン化型検出器）
使用カラム：ＤＢ−１７０１（長さ：５０ｍ、膜厚１μｍ、内径０．３２ｍｍ）（アジレント・テクノロジー株式会社製）
分析条件：Ｉｎｊｅｃｔ．Ｔｅｍｐ．２５０℃、Ｄｅｔｅｃｔ．Ｔｅｍｐ．２５０℃
昇温条件：７０℃→（５℃／分で昇温）→２５０℃
内部標準物質：ジグライム（ジエチレングリコールジメチルエーテル）[Gas chromatography analysis]
Analytical instrument: GC-14A (manufactured by Shimadzu Corporation)
Detector: FID (hydrogen flame ionization detector)
Column used: DB-1701 (length: 50 m, film thickness 1 μm, inner diameter 0.32 mm) (manufactured by Agilent Technologies, Inc.)
Analysis conditions: Inject. Temp. 250 ° C., Detect. Temp. 250 ° C
Temperature rising condition: 70 ° C → (temperature rising at 5 ° C / min) → 250 ° C
Internal standard substance: diglyme (diethylene glycol dimethyl ether)

Figure 2018003624
Figure 2018003624

１０時間後、ＳＡＬは９９．９％が残存していたのに対し、アクロレインは安定剤としてヒドロキノンを含有するにも関わらず３．４％が失われていた。この結果から、ＳＡＬはアクロレインよりも極めて熱安定性が高いことがわかる。   After 10 hours, 99.9% of SAL remained, whereas 3.4% of acrolein was lost despite containing hydroquinone as a stabilizer. From this result, it can be seen that SAL has extremely high thermal stability than acrolein.

＜試験例２＞ｐＨ安定性試験
ＳＡＬおよびアクロレインをそれぞれｐＨの異なる０．５ｍｏｌ／Ｌリン酸緩衝液に溶解させ、０．１ｗｔ％溶液を調製した。該溶液５０ｍＬを窒素雰囲気下でサンプル瓶に入れ、２３±２℃で保管し、調製時のＳＡＬおよびアクロレインの含有量を１００％とした際の含有率の変化を、高速液体クロマトグラフィー分析による絶対検量線で観察した。結果を図１および２に示す。
この結果から、ＳＡＬはアクロレインよりも極めてｐＨ安定性が高いことがわかる。<Test Example 2> pH Stability Test SAL and acrolein were dissolved in 0.5 mol / L phosphate buffer solutions different in pH to prepare a 0.1 wt% solution. 50 mL of the solution was put in a sample bottle under nitrogen atmosphere, stored at 23 ± 2 ° C., and the change in content when making the contents of SAL and acrolein at the time of preparation 100% was absolute by high performance liquid chromatography analysis It observed by the calibration curve. The results are shown in FIGS. 1 and 2.
From this result, it can be seen that SAL has extremely high pH stability than acrolein.

［リン酸緩衝液の調製］
ｐＨ１．７：７５％リン酸４．９ｇ、リン酸二水素ナトリウム・２水和物７．８ｇを蒸留水２００ｍＬに溶解させた。
ｐＨ６．２：リン酸二水素ナトリウム・２水和物７．８ｇ、リン酸水素二ナトリウム７．１ｇを蒸留水２００ｍＬに溶解させた。
ｐＨ８．１：リン酸二水素ナトリウム・２水和物０．３ｇ、リン酸水素二ナトリウム１３．９ｇを蒸留水２００ｍＬに溶解させた。[Preparation of phosphate buffer solution]
pH 1.7: 4.9 g of phosphoric acid 4.9 g, and sodium dihydrogen phosphate dihydrate 7.8 g were dissolved in 200 mL of distilled water.
pH 6.2: 7.8 g of sodium dihydrogen phosphate dihydrate and 7.1 g of disodium hydrogen phosphate were dissolved in 200 mL of distilled water.
pH 8.1: 0.3 g of sodium dihydrogen phosphate dihydrate and 13.9 g of disodium hydrogen phosphate were dissolved in 200 mL of distilled water.

［高速液体クロマトグラフィー分析］
分析機器：Ｐｒｏｍｉｎｅｎｃｅシステム（株式会社島津製作所製）
使用カラム：Ｃａｄｅｎｚａ ＣＤ−Ｃ１８（長さ：１５０ｍ、内径４．６ｍｍ）
展開液：Ｈ２Ｏ／ＭｅＯＨ＝４５／５５ｖｏｌ比、Ｈ３ＰＯ４＝１ｍｏｌ／Ｌ
流速：１ｍＬ／ｍｉｎ[High-performance liquid chromatography analysis]
Analytical instrument: Prominence system (made by Shimadzu Corporation)
Column used: Cadenza CD-C18 (length: 150 m, internal diameter 4.6 mm)
Developer: H 2 O / MeOH = 45/55 vol ratio, H 3 PO 4 = 1 mol / L
Flow rate: 1 mL / min

＜参考例＞
ＳＡＬ、シトラールおよびアクロレインは既存化合物であり、安全性に関する情報は開示されている。参考として、安全性に関する情報を表２に示す。ＳＡＬやシトラールはアクロレインと比べ毒性が極めて低く、安全であることがわかる。<Reference example>
SAL, citral and acrolein are existing compounds, and safety information is disclosed. Information on safety is shown in Table 2 for reference. SAL and citral have extremely low toxicity compared to acrolein and prove to be safe.

Figure 2018003624
Figure 2018003624

以上の実施例、比較例、試験例および参考例から、ＳＡＬ等のアルデヒド（１）はアクロレインと同等の硫化鉄除去能力を有し、アクロレインよりも熱安定性およびｐＨ安定性が高く、かつ安全であることがわかる。   From the above examples, comparative examples, test examples and reference examples, aldehyde (1) such as SAL has the same iron sulfide removal ability as acrolein, and has higher thermal stability and pH stability than acrolein, and it is safe It can be seen that it is.

本発明の組成物は熱安定性およびｐＨ安定性が高く、硫化鉄を安全に効率よく除去できる点で有用である。   The composition of the present invention is useful in that it has high thermal stability and pH stability and can safely and efficiently remove iron sulfide.

Claims (7)

下記一般式（１）で表されるα，β−不飽和アルデヒドを有効成分として含有する、硫化鉄除去用の組成物。
Figure 2018003624
 （Ｒ１〜Ｒ３はそれぞれ独立して水素原子、炭素数１〜１０のアルキル基、炭素数２〜１０のアルケニル基または炭素数６〜１２のアリール基を表す。ただし、Ｒ１はＲ２またはＲ３と互いに連結して炭素数２〜６のアルキレン基を構成してもよく、Ｒ１とＲ２が同時に水素原子であることはない。）The composition for iron sulfide removal which contains the (alpha), (beta)-unsaturated aldehyde represented by following General formula (1) as an active ingredient.
Figure 2018003624
 (R 1 to R 3 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, provided that R 1 is R 2 Or R 3 may be linked to each other to form an alkylene group having 2 to 6 carbon atoms, and R 1 and R 2 may not simultaneously be a hydrogen atom.) Ｒ１〜Ｒ３がそれぞれ独立して水素原子または炭素数１〜５のアルキル基である、請求項１に記載の組成物。The composition according to claim 1, wherein each of R 1 to R 3 independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Ｒ３が水素原子である、請求項１または２に記載の組成物。The composition according to claim 1 or 2, wherein R 3 is a hydrogen atom. 請求項１〜３のいずれかに記載の組成物を硫化鉄に接触させることを特徴とする、硫化鉄の除去方法。   A method for removing iron sulfide, comprising bringing the composition according to any one of claims 1 to 3 into contact with iron sulfide. 前記組成物中のα，β−不飽和アルデヒドを、硫化鉄１質量部に対し０．１〜１００質量部となるように添加する、請求項４に記載の方法。   The method according to claim 4, wherein the α, β-unsaturated aldehyde in the composition is added in an amount of 0.1 to 100 parts by mass with respect to 1 part by mass of iron sulfide. 前記組成物中のα，β−不飽和アルデヒドと硫化鉄を−３０℃〜１５０℃の範囲で接触させることを特徴とする、請求項４または５に記載の方法。   The method according to claim 4 or 5, characterized in that the α, β-unsaturated aldehyde and iron sulfide in the composition are brought into contact in the range of -30 ° C to 150 ° C. 硫化鉄を除去するための、請求項１〜３のいずれかに記載の組成物の使用。   Use of the composition according to any of claims 1 to 3 for removing iron sulfide.
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