WO2018003624A1 - Composition for removing iron sulfide - Google Patents

Composition for removing iron sulfide Download PDF

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Publication number
WO2018003624A1
WO2018003624A1 PCT/JP2017/022837 JP2017022837W WO2018003624A1 WO 2018003624 A1 WO2018003624 A1 WO 2018003624A1 JP 2017022837 W JP2017022837 W JP 2017022837W WO 2018003624 A1 WO2018003624 A1 WO 2018003624A1
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group
iron sulfide
methyl
composition
carbon atoms
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PCT/JP2017/022837
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French (fr)
Japanese (ja)
Inventor
将貴 清水
勇祐 齊藤
拓大 ▲鶴▼田
純市 藤
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株式会社クラレ
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Priority to JP2018525091A priority Critical patent/JPWO2018003624A1/en
Priority to BR112018076690-9A priority patent/BR112018076690A2/en
Priority to EP17819983.2A priority patent/EP3486353A4/en
Priority to US16/312,363 priority patent/US20190241822A1/en
Priority to CA3028940A priority patent/CA3028940A1/en
Priority to SG11201811541TA priority patent/SG11201811541TA/en
Priority to MX2018016415A priority patent/MX2018016415A/en
Priority to RU2018145752A priority patent/RU2018145752A/en
Priority to CN201780038445.0A priority patent/CN109415819A/en
Publication of WO2018003624A1 publication Critical patent/WO2018003624A1/en

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
    • C10G75/02—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general by addition of corrosion inhibitors
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/12—Organic compounds only
    • C10G21/16—Oxygen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/20—Organic compounds not containing metal atoms
    • C10G29/22—Organic compounds not containing metal atoms containing oxygen as the only hetero atom
    • C10G29/24—Aldehydes or ketones
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/14—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means
    • C10G9/16—Preventing or removing incrustation
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/24—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents

Definitions

  • the present invention relates to a composition for removing iron sulfide and a method for removing iron sulfide using the same.
  • Natural gas liquefied natural gas, sour gas, crude oil, naphtha, heavy aromatic naphtha, gasoline, kerosene, diesel oil, light oil, heavy oil, FCC slurry, asphalt, hydrocarbons such as refined petroleum products such as oilfield concentrate
  • the hydrogen sulfide often present therein corrodes iron used in excavation facilities and the like, and causes iron sulfide to be generated. Iron sulfide accumulates as deposits in production facilities for fossil fuels and refined petroleum products to reduce the operational efficiency of equipment such as heat exchangers, cooling towers, reaction vessels, transport pipelines or furnaces, and to maintain equipment. It is desirable to remove this because it interferes with accurate measurement.
  • acrolein As a method of removing iron sulfide, a method of dissolving iron sulfide using acrolein is known, and SPE Annual Technical Conference and Exhibition opened in Denver, Colorado from October 30 to November 2, 2011. SPE 146080 has also been announced regarding iron sulfide removal with acrolein as an active ingredient.
  • acrolein is highly toxic and is a compound whose concentration is strictly regulated in terms of occupational safety and environmental safety, and there is a problem that it requires careful handling.
  • acrolein is extremely easy to polymerize and lacks thermal stability, and lacks pH stability, and the abundance gradually decreases depending on the pH of the environment in which it is used. .
  • 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 removing iron sulfide safely and efficiently.
  • aldehyde (1) A composition for removing iron sulfide containing an ⁇ , ⁇ -unsaturated aldehyde (hereinafter referred to as aldehyde (1)) represented by the following general formula (1) as an active ingredient.
  • R 1 to R 3 each independently represents 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 represents R 2 (Alternatively, they may be linked to R 3 to form an alkylene group having 2 to 6 carbon atoms, and R 1 and R 2 are not simultaneously hydrogen atoms.)
  • R 1 to R 3 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • R 3 The composition of [1] or [2], wherein R 3 is a hydrogen atom.
  • [4] A method for removing iron sulfide, comprising bringing the composition according to any one of [1] to [3] into contact with iron sulfide. [5] The method of [4], wherein the aldehyde (1) in the composition is added so as to be 0.1 to 100 parts by mass with respect to 1 part by mass of iron sulfide. [6] The method of [4] or [5], wherein the aldehyde (1) and iron sulfide in the composition are contacted 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.
  • the composition of this invention is excellent in the removal performance of iron sulfide by containing aldehyde (1).
  • the composition of the present invention has the advantages of extremely low toxicity, high thermal stability and pH stability compared to conventional iron sulfide removal agents containing acrolein.
  • aldehyde (1) has at least one alkyl group, alkenyl group or aryl group at the ⁇ -position, it can be compared to acrolein which does not have a substituent at the ⁇ -position. It is thought that one of the factors is that the addition reaction to a ⁇ -position of a bulky molecule such as is difficult to occur.
  • the composition of the present invention is characterized by containing aldehyde (1) as an active ingredient.
  • the alkyl group having 1 to 10 carbon atoms independently represented by R 1 to R 3 may be linear, branched or cyclic, for example, methyl group, ethyl group, n-propyl group, isopropyl group 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.
  • 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 more preferable.
  • the alkenyl group having 2 to 10 carbon atoms independently represented by R 1 to R 3 may be linear, branched or cyclic, such as vinyl group, allyl group, 1-penten-1-yl group, 4-methyl Examples include a -3-penten-1-yl group, a 4-penten-1-yl group, a 1-hexen-1-yl group, a 1-octen-1-yl group, and a 1-decene-1-yl group.
  • an alkenyl group having 1 to 8 carbon atoms is preferable, and an alkenyl group having 1 to 6 carbon atoms is more preferable.
  • the aryl group having 6 to 12 carbon atoms independently represented by R 1 to R 3 include a phenyl group, a tolyl group, an ethylphenyl group, a xylyl group, a trimethylphenyl group, a naphthyl group, and a biphenylyl group. Of these, aryl groups having 6 to 10 carbon atoms are preferred.
  • R 1 When R 1 is connected to R 2 or R 3 to represent an alkylene group having 2 to 6 carbon atoms, examples of the alkylene group include an ethylene group, an n-propylene group, an n-butylene group, and an 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. Is mentioned.
  • R 1 to R 3 are preferably each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • R 1, R 2 is a methyl group, in R 1, R 2 are both methyl groups More preferably.
  • R 3 is preferably a hydrogen atom.
  • aldehyde (1) examples 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,
  • 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 are preferred, 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.
  • SAL 3-methyl-2-butenal
  • SAL 3-methyl-2-butenal
  • SAL senecioaldehyde
  • Aldehyde (1) may be a commercially available product or may be synthesized by oxidative dehydrogenation of the corresponding ⁇ , ⁇ -unsaturated alcohol (see, for example, JP-A-60-224652).
  • the content ratio of the aldehyde (1) which is an active ingredient in the composition of the present invention can be appropriately set according to the use mode, but is usually 1 to 99.9% by mass, from the viewpoint of cost effectiveness.
  • the amount is preferably 5 to 99.9% by mass, more preferably 5 to 95% by mass.
  • the composition of the present invention may contain other iron sulfide removing agents such as acrolein, tetrakis (hydroxymethyl) phosphine or a corresponding phosphonium salt, hydrochloric acid, formic acid and the like as long as the effects of the present invention are not impaired.
  • the composition of the present invention contains a suitable solvent such as cyclohexane, toluene, xylene, heavy aromatic naphtha, petroleum distillate; monoalcohol or diol having 1 to 10 carbon atoms such as methanol, ethanol, ethylene glycol; You may do it.
  • composition of the present invention is a surfactant, corrosion inhibitor, oxygen scavenger, iron control agent, crosslinking agent, breaker, flocculant, temperature stabilizer, as long as the effects of the present invention are not impaired, in addition to the aldehyde (1).
  • the manufacturing method of the composition of this invention is not specifically limited, For example, it can manufacture by adding arbitrary components, such as said other iron sulfide removal agent and a solvent, to aldehyde (1), and mixing.
  • the composition of the present invention is preferably in a liquid state, it may be appropriately supported on a carrier or the like according to the form used for removing iron sulfide, and may be in a solid state such as powder or fluid.
  • an amount of the composition of the present invention sufficient for removing iron sulfide is added to a liquid containing iron sulfide for treatment.
  • the amount of aldehyde (1) contained in the composition of the present invention is preferably 0.1 to 1 part by weight of iron sulfide. Add 100 parts by mass, more preferably 2 to 100 parts by mass.
  • the temperature at which the composition of the present invention is added to and brought into contact with a liquid containing iron sulfide to perform the treatment is preferably in the range of 0 ° C. to 150 ° C., more preferably in the range of 20 ° C. to 130 ° C.
  • SAL synthesized from prenol according to the method described in JP-A-60-224652 (purity 98.1%)
  • Acrolein manufactured by Tokyo Chemical Industry Co., Ltd., containing hydroquinone as a stabilizer
  • Example 1 Iron sulfide removal test (SAL) 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 hydrate in a 1 L three-necked flask equipped with a thermometer, stirrer and condenser When 138.2 (0.5 mmol) was added and stirred, iron sulfide was produced as a fine black precipitate. Thereto, 126.3 mg (1.5 mmol) of SAL was added, and the temperature of the reaction solution was raised to 50 ° C. while stirring at 500 rpm. The time when SAL was added was set to 0 hour, and the state of iron sulfide was observed. As a result, after 4 hours, iron sulfide was dissolved and the reaction solution became colorless and transparent.
  • SAL Iron sulfide removal test
  • Example 2 Iron sulfide removal test (citral) A test similar to Example 1 was performed except that citral was used instead of SAL. After 7 hours, iron sulfide was dissolved and the reaction solution became colorless and transparent.
  • Example 1 Iron sulfide removal test (Acrolein) The same test as in Example 1 was performed except that acrolein was used instead of SAL. After 4 hours, iron sulfide was dissolved, and the reaction solution became colorless and transparent.
  • SAL, citral and acrolein are existing compounds and safety information is disclosed.
  • Table 2 shows information related to safety. SAL and citral are extremely toxic compared to acrolein and are safe.
  • aldehyde (1) such as SAL has iron sulfide removal ability equivalent to acrolein, and has higher thermal stability and pH stability than acrolein, and is safe. It can be seen that it is.
  • 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.

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Abstract

Provided is a composition for removing iron sulfide, the composition containing an α,β-unsaturated aldehyde represented by general formula (1) as an active ingredient (wherein: R1-R3 each independently represent a hydrogen atom, an alkyl group having 1-10 carbon atoms, an alkenyl group having 2-10 carbon atoms, or an aryl group having 6-12 carbon atoms; R1 may be bonded with R2 or R3 to form an alkylene group having 2-6 carbon atoms; and R1 and R2 would not simultaneously be hydrogen atoms).

Description

硫化鉄除去用の組成物Composition for removing iron sulfide
　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, light oil, heavy oil, FCC slurry, asphalt, hydrocarbons such as refined petroleum products such as oilfield concentrate The hydrogen sulfide often present therein corrodes iron used in excavation facilities and the like, and causes iron sulfide to be generated. Iron sulfide accumulates as deposits in production facilities for fossil fuels and refined petroleum products to reduce the operational efficiency of equipment such as heat exchangers, cooling towers, reaction vessels, transport pipelines or furnaces, and to maintain equipment. It is desirable to remove this because 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 opened in Denver, Colorado from October 30 to November 2, 2011. SPE 146080 has also been announced regarding iron sulfide removal with acrolein as an active ingredient. However, acrolein is highly toxic and is a 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 extremely easy to polymerize and lacks thermal stability, and lacks pH stability, and the abundance gradually decreases depending on the pH of the environment in which it is used. .
　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 described above, the use of acrolein for the purpose of removing iron sulfide has problems in terms of safety, thermal stability, and pH stability, and replacement with a safer and more 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 removing iron sulfide safely and efficiently.
　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 object is achieved by the following [1] to [7].
[1] A composition for removing iron sulfide containing an α, β-unsaturated aldehyde (hereinafter referred to as aldehyde (1)) represented by the following general formula (1) as an active ingredient.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
（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 represents 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 represents R 2 (Alternatively, they may be linked to R 3 to form an alkylene group having 2 to 6 carbon atoms, and R 1 and R 2 are not simultaneously hydrogen atoms.)
[2] The composition of [1], wherein R 1 to R 3 are each independently 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 the composition according to any one of [1] to [3] into contact with iron sulfide.
[5] The method of [4], wherein the aldehyde (1) in the composition is added so as to be 0.1 to 100 parts by mass with respect to 1 part by mass of iron sulfide.
[6] The method of [4] or [5], wherein the aldehyde (1) and iron sulfide in the composition are contacted 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 this invention is excellent in the removal performance of iron sulfide by containing aldehyde (1).
In particular, the composition of the present invention has the advantages of extremely low toxicity, high thermal stability and pH stability compared to conventional iron sulfide removal agents containing acrolein. The reason for this is not always clear, but since aldehyde (1) has at least one alkyl group, alkenyl group or aryl group at the β-position, it can be compared to acrolein which does not have a substituent at the β-position. It is thought that one of the factors is that the addition reaction to a β-position of a bulky molecule such as is difficult to occur. On the other hand, with regard to the removal of iron sulfide, it is considered that by combining with hydrogen sulfide in equilibrium with iron sulfide and removing this, dissolution of iron sulfide is promoted, and as a result, iron sulfide is removed. Even if it has a substituent at the β-position, attack from hydrogen sulfide, which is generally a small molecule, is not so hindered, and it is considered that the 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 the pH stability of senesioaldehyde (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 aldehyde (1) as an active ingredient.
In the aldehyde (1), the alkyl group having 1 to 10 carbon atoms independently represented by R 1 to R 3 may be linear, branched or cyclic, for example, methyl group, ethyl group, n-propyl group, isopropyl group 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. From the viewpoint of iron sulfide removal performance, 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 more preferable.
The alkenyl group having 2 to 10 carbon atoms independently represented by R 1 to R 3 may be linear, branched or cyclic, such as vinyl group, allyl group, 1-penten-1-yl group, 4-methyl Examples include a -3-penten-1-yl group, a 4-penten-1-yl group, a 1-hexen-1-yl group, a 1-octen-1-yl group, and a 1-decene-1-yl group. Of these, an alkenyl group having 1 to 8 carbon atoms is preferable, and an alkenyl group having 1 to 6 carbon atoms is more preferable.
Examples of the aryl group having 6 to 12 carbon atoms independently represented by R 1 to R 3 include a phenyl group, a tolyl group, an ethylphenyl group, a xylyl group, a trimethylphenyl group, a naphthyl group, and a biphenylyl group. Of these, aryl groups having 6 to 10 carbon atoms are preferred.
When R 1 is connected to R 2 or R 3 to represent an alkylene group having 2 to 6 carbon atoms, examples of the alkylene group include an ethylene group, an n-propylene group, an n-butylene group, and an 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. Is mentioned.
R 1 to R 3 are preferably each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
A performance of removing iron sulfide, and from the viewpoint of securing the thermal stability and pH stability, it is preferable that at least one of R 1, R 2 is a methyl group, in R 1, R 2 are both methyl groups More preferably.
Moreover, 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- 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-isobu 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-isopropyl-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 -Dimethyl Lucyclohexene, 1-formyl-5,5-dimethylcyclohexene, 1-formyl-2methylcyclohexene, 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-oct 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, And 3-naphthylpropenal. 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 are preferred, 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 a trans body and a cis body, either 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 oxidative dehydrogenation 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。 The content ratio of the aldehyde (1) which is an active ingredient in the composition of the present invention can be appropriately set according to the use mode, but is usually 1 to 99.9% by mass, from the viewpoint of cost effectiveness. The amount is preferably 5 to 99.9% by mass, more preferably 5 to 95% by 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 a corresponding phosphonium salt, hydrochloric acid, formic acid and the like as long as the effects of the present invention are not impaired.
The composition of the present invention contains a suitable solvent such as cyclohexane, toluene, xylene, heavy aromatic naphtha, petroleum distillate; monoalcohol or diol having 1 to 10 carbon atoms such as methanol, ethanol, ethylene glycol; You may do it.
　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 a surfactant, corrosion inhibitor, oxygen scavenger, iron control agent, crosslinking agent, breaker, flocculant, temperature stabilizer, as long as the effects of the present invention are not impaired, in addition to the aldehyde (1). , PH adjusters, dehydration adjusters, anti-swelling agents, scale inhibitors, biocides, friction reducers, antifoaming agents, anti-mudging 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 manufacturing method of the composition of this invention is not specifically limited, For example, it can manufacture by adding arbitrary components, such as said other iron sulfide removal agent and a solvent, to aldehyde (1), and mixing.
Although the composition of the present invention is preferably in a liquid state, it may be appropriately supported on a carrier or the like according to the form used for removing iron sulfide, and may be in a solid state 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, an amount of the composition of the present invention sufficient for removing iron sulfide is added to a liquid containing iron sulfide for treatment. In the method for 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 weight of iron sulfide. Add 100 parts by mass, more preferably 2 to 100 parts by mass. The temperature at which the composition of the present invention is added to and brought into contact with a liquid containing iron sulfide to perform the treatment is preferably in the range of 0 ° C. to 150 ° C., more preferably in the range of 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 EXAMPLES Hereinafter, although an Example etc. demonstrate this invention concretely, this invention is not limited at all by the following examples. In addition, 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: manufactured 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)
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 hydrate in a 1 L three-necked flask equipped with a thermometer, stirrer and condenser When 138.2 (0.5 mmol) was added and stirred, iron sulfide was produced as a fine black precipitate. Thereto, 126.3 mg (1.5 mmol) of SAL was added, and the temperature of the reaction solution was raised to 50 ° C. while stirring at 500 rpm. The time when SAL was added was set to 0 hour, and the state of iron sulfide was observed. As a result, after 4 hours, 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)
A test similar to Example 1 was performed except that citral was used instead of SAL. After 7 hours, iron sulfide was 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 performed except that acrolein was used instead of SAL. After 4 hours, iron sulfide was 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 SAL and acrolein are each placed in a 50 mL three-necked flask, heated to 50 ° C. in a nitrogen atmosphere, and the content ratio when the SAL and acrolein content immediately after the heating is 100%. 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)
Analysis conditions: Inject. Temp. 250 ° C., Detect. Temp. 250 ° C
Temperature rising condition: 70 ° C → (heated at 5 ° C / min) → 250 ° C
Internal reference material: diglyme (diethylene glycol dimethyl ether)
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　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 acrolein lost 3.4% despite containing hydroquinone as a stabilizer. From this result, it can be seen that SAL has extremely higher 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 having different pHs to prepare 0.1 wt% solutions. 50 mL of the solution was placed in a sample bottle under a nitrogen atmosphere and stored at 23 ± 2 ° C., and the change in the content rate when the SAL and acrolein content during preparation was 100% was determined by high performance liquid chromatography analysis. Observation was made with a calibration curve. The results are shown in FIGS.
This result shows that SAL has extremely higher 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]
pH 1.7: 4.9 g of 75% phosphoric acid and 7.8 g of sodium dihydrogen phosphate dihydrate 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 (manufactured by Shimadzu Corporation)
Column used: Cadenza CD-C18 (length: 150 m, inner diameter 4.6 mm)
Developing solution: 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. As a reference, Table 2 shows information related to safety. SAL and citral are extremely toxic compared to acrolein and are safe.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　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 iron sulfide removal ability equivalent to acrolein, and has higher thermal stability and pH stability than acrolein, and 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)

  1. 　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 JPOXMLDOC01-appb-C000001
     （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。）     A composition for removing iron sulfide containing an α, β-unsaturated aldehyde represented by the following general formula (1) as an active ingredient.
    Figure JPOXMLDOC01-appb-C000001
     (R 1 to R 3 each independently represents 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 represents R 2 (Alternatively, they may be linked to R 3 to form an alkylene group having 2 to 6 carbon atoms, and R 1 and R 2 are not simultaneously hydrogen atoms.)
  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、請求項１に記載の組成物。 The composition according to claim 1, wherein R 1 to R 3 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  3. 　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.
  4. 　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 contacting the composition according to any one of claims 1 to 3 with iron sulfide.
  5. 　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 so as to be 0.1 to 100 parts by mass with respect to 1 part by mass of iron sulfide.
  6. 　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。 6. The method according to claim 4 or 5, wherein the α, β-unsaturated aldehyde and iron sulfide in the composition are contacted in the range of −30 ° C. to 150 ° C.
  7. 　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 one of claims 1 to 3 for removing iron sulfide.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019124340A1 (en) * 2017-12-22 2019-06-27 株式会社クラレ Treatment agent for extraction of crude oil or natural gas

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60224652A (en) 1984-04-23 1985-11-09 Kuraray Co Ltd Production of 3-methyl-2-buten-1-al
JPH11241194A (en) * 1998-02-27 1999-09-07 Jgc Corp Method for washing apparatus deposited with heavy hydrocarbon based sludge and piping structure for washing

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2402615A (en) * 1940-09-19 1946-06-25 Du Pont Catalytic process and products thereof
US2571739A (en) * 1949-10-28 1951-10-16 Pure Oil Co Prevention of corrosion of structural metals by hydrogen sulfide, air, and water
US4400368A (en) * 1981-11-24 1983-08-23 Shell Oil Company H2 S Removal process
US4734259A (en) * 1985-11-22 1988-03-29 Dowell Schlumberger Incorporated Mixtures of α,β-unsaturated aldehides and surface active agents used as corrosion inhibitors in aqueous fluids
US6086056A (en) * 1998-04-29 2000-07-11 Leask; Jim Float sink header
US6068056A (en) * 1999-10-13 2000-05-30 Schlumberger Technology Corporation Well treatment fluids comprising mixed aldehydes
US6436880B1 (en) * 2000-05-03 2002-08-20 Schlumberger Technology Corporation Well treatment fluids comprising chelating agents
US6887840B2 (en) * 2003-01-21 2005-05-03 Milborn Enterprises Llc Iron sulfide clean-up composition and method
US20080227669A1 (en) * 2007-03-12 2008-09-18 Halliburton Energy Services, Inc. Corrosion-inhibiting additives, treatment fluids, and associated methods
US20080227668A1 (en) * 2007-03-12 2008-09-18 Halliburton Energy Services, Inc. Corrosion-inhibiting additives, treatment fluids, and associated methods
US7855171B2 (en) * 2008-10-16 2010-12-21 Trahan David O Method and composition to remove iron and iron sulfide compounds from pipeline networks
PL2611310T3 (en) * 2010-08-27 2017-12-29 Anitox Corporation Antimicrobial formulation
US20130261032A1 (en) * 2012-03-29 2013-10-03 Schlumberger Technology Corporation Additive for subterranean treatment
JP5951426B2 (en) * 2012-09-14 2016-07-13 株式会社Ｊ−オイルミルズ Cholecystokinin secretion promoting composition
CN103194325B (en) * 2013-04-25 2014-09-10 甘肃黑马石化工程有限公司 Ferrous sulfide dirt neutral complexing cleaning agent and preparation method thereof
WO2015142642A1 (en) * 2014-03-19 2015-09-24 Enersciences Holdings, Llc Methods and apparatus for treating sulfides in produced fluids
WO2018003623A1 (en) * 2016-06-28 2018-01-04 株式会社クラレ Composition for removing sulfur-containing compound

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60224652A (en) 1984-04-23 1985-11-09 Kuraray Co Ltd Production of 3-methyl-2-buten-1-al
JPH11241194A (en) * 1998-02-27 1999-09-07 Jgc Corp Method for washing apparatus deposited with heavy hydrocarbon based sludge and piping structure for washing

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
See also references of EP3486353A4 *
SPE ANNUAL TECHNICAL CONFERENCE AND EXHIBITION SPE 146080, 2011, Retrieved from the Internet <URL:http://dx.doi.org/10.2118/146080-MS>
SPE ANNUAL TECHNICAL CONFERENCE AND EXHIBITION SPE 146080, 30 October 2011 (2011-10-30)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019124340A1 (en) * 2017-12-22 2019-06-27 株式会社クラレ Treatment agent for extraction of crude oil or natural gas

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