WO2019124340A1

WO2019124340A1 - Treatment agent for extraction of crude oil or natural gas

Info

Publication number: WO2019124340A1
Application number: PCT/JP2018/046484
Authority: WO
Inventors: 将貴清水; 拓大 ▲鶴▼田; 勇祐齊藤
Original assignee: 株式会社クラレ
Priority date: 2017-12-22
Filing date: 2018-12-18
Publication date: 2019-06-27
Also published as: TW201928002A

Abstract

A treatment agent for the extraction of crude oil or natural gas, the treatment agent including 1–30 mass% of a γ,δ-unsaturated alcohol that is represented by general formula (1) and 50–97 mass% of an α,β-unsaturated aldehyde that is represented by general formula (2).

Description

Treatment agent for crude oil or natural gas

The present invention relates to a crude oil or natural gas processing agent for mining.

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 Often include sulfur containing compounds such as hydrogen sulfide and various compounds containing -SH groups (typically various mercaptans). The toxicity of hydrogen sulfide is well known, and in the fossil fuel and refined petroleum product industries, considerable expense and effort are being made to reduce the hydrogen sulfide content to safe levels. For example, for pipeline gas, it is required as a general regulation value that the content of hydrogen sulfide does not exceed 4 ppm. Also, various compounds containing hydrogen sulfide and -SH groups tend to be released into the vapor space due to their volatility, in which case their offensive odor may be stored in or around hydrocarbon storage pipelines , And has become a problem through the shipping system.
Moreover, hydrogen sulfide corrodes iron used for a drilling facility etc., and causes iron sulfide to be generated. Iron sulfide accumulates as deposits in facilities for producing fossil fuels and refined petroleum products, and reduces the operating 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 the accurate measurement of
On the other hand, in recent years, in the mining of fossil fuels (for example, petroleum, natural gas, shale oil, shale gas, etc.) crushing of bedrock by high pressure water, etc. have been carried out. Corrosion is seen. Biocorrosion refers to a corrosion phenomenon induced directly or indirectly by the action of microorganisms present in the environment, and although many research examples have been reported (for example, Non-Patent Document 1), There is still an unexplained part regarding the mechanism etc. Recent studies have shown that when biocorrosion is caused by two or more microorganisms (eg, sulfate reducing bacteria and methanogenic bacteria), the action of these microorganisms may synergistically promote corrosion. Has been reported.

Methods of removing hydrogen sulfide and iron sulfide and the use of acrolein as an effective component for sterilizing microorganisms are disclosed (for example, Patent Documents 1 to 3). In addition, SPE Annual Technical Conference and Exhibition SPE 146080, which was held from October 30 to November 2, 2011 in Denver, Colorado, USA, presented iron sulfide removal, hydrogen sulfide removal, and bactericidal agents containing acrolein as the active ingredient. (Non-Patent Document 2). 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. .

U.S. Pat. No. 4,680,127 U.S. Pat. No. 3,459,852 U.S. Pat. No. 2,987,475

As described above, using acrolein for the purpose of removing iron sulfide and sulfur-containing compounds or sterilizing microorganisms has problems in terms of safety, thermal stability, and pH stability, and is safer and more stable. Substitution by compounds is desired.

Therefore, the object of the present invention is to provide an active component having high thermal stability and pH stability, and to safely and efficiently remove iron sulfide and sulfur-containing compounds, and to have excellent sterilization properties. It is providing a processing agent which controls biocorrosion.

As a result of earnest studies to solve the above problems, the present inventors considered the present invention described below and found that the problems can be solved.
That is, the present invention is as follows.

[1] 1 to 30% by mass of a γ, δ-unsaturated alcohol represented by the following general formula (1), and 50 to 97 mass of an α, β-unsaturated aldehyde represented by the following general formula (2) Processing agents for crude oil or natural gas mining including%.

In the general formula (1), R ¹ to R ⁴ 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. However, R ¹ and R ³ or R ² and R ⁴ may be connected to each other to form an alkylene group having 2 to 6 carbon atoms.

In (formula (2), .R ⁷ represents an alkyl group, an alkenyl group or an aryl group having 6 to 12 carbon atoms having 2 to 10 carbon atoms of ^{R 5} and ^{R 6} are 1 to 10 carbon atoms each independently And a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, provided that R ⁵ and R ⁶ or R ⁵ and R ⁷ may be connected to each other to form an alkylene group having 2 to 6 carbon atoms.
[2] The treating agent according to the above [1], wherein R ⁷ is a hydrogen atom.
[3] The treatment agent according to the above [1] or [2] for removing iron sulfide.
[4] A method of removing iron sulfide by bringing the treating agent according to [3] into contact with iron sulfide.
[5] The treatment agent is brought into contact with the iron sulfide such that the α, β-unsaturated aldehyde in the treatment agent is 0.1 to 100 parts by mass with respect to 1 part by mass of the iron sulfide. 4].
[6] The method according to [4] or [5] above, wherein the treatment agent and the iron sulfide are brought into contact in the range of −30 ° C. to 150 ° C.
[7] Use of the treating agent according to the above [3] for removing iron sulfide.
[8] A treating agent for removing a sulfur-containing compound in a liquid or gas, wherein the sulfur-containing compound is a compound containing hydrogen sulfide, a —SH group, or a mixture thereof. The treatment agent as described in 2].
[9] The treating agent according to the above [8], wherein the liquid or gas is a hydrocarbon.
[10] The liquid or gas is a group consisting of natural gas, liquefied natural gas, sour gas, crude oil, naphtha, heavy aromatic naphtha, gasoline, kerosene, diesel oil, light oil, heavy oil, FCC slurry, asphalt and oil field concentrate The processing agent according to the above [8], which is at least one selected from
[11] A method for removing a sulfur-containing compound in a liquid or gas, wherein the sulfur-containing compound is hydrogen sulfide, a compound containing a —SH group, or a mixture thereof, of the above-mentioned [8] to [10] Contacting the treatment agent according to any of the above with the liquid or gas.
[12] The method according to [11] above, wherein the liquid or gas is a hydrocarbon.
[13] The liquid or gas is a group consisting of natural gas, liquefied natural gas, sour gas, crude oil, naphtha, heavy aromatic naphtha, gasoline, kerosene, diesel oil, light oil, heavy oil, FCC slurry, asphalt and oil field concentrate The method according to [11] above, which is at least one selected from
[14] The treating agent is contacted with the liquid or gas such that the α, β-unsaturated aldehyde contained in the treating agent is 0.1 to 100 parts by mass with respect to 1 part by mass of the sulfur-containing compound. The method according to any one of the above [11] to [13].
[15] The method according to any one of the above [11] to [14], wherein the treatment agent and the liquid or gas are brought into contact in the range of −30 ° C. to 150 ° C.
[16] The treatment agent according to any one of the above [8] to [10] for removing a sulfur-containing compound that is hydrogen sulfide in liquid or gas, a compound containing an —SH group, or a mixture thereof use.
[17] The treatment agent according to the above [1] or [2], which is for suppressing biocorrosion of metal.
[18] A sterilizing method using the treatment agent according to [17].
[19] Use of the treatment agent according to the above [17] as a biocorrosion inhibitor which suppresses biocorrosion of metal.

According to the present invention, thermal stability is achieved by containing the γ, δ-unsaturated alcohol represented by the general formula (1) and the α, β-unsaturated aldehyde represented by the general formula (2). And an active component having high pH stability and capable of safely and efficiently removing iron sulfide and sulfur-containing compounds, and providing a treating agent capable of suppressing metal biocorrosion by having excellent bactericidal properties it can.

It is a graph which shows pH stability of a senesio aldehyde (SAL). It is a graph which shows the pH stability of acrolein.

The crude oil or natural gas mining treatment agent (hereinafter sometimes referred to as “treatment agent”) of the present invention is a γ, δ-unsaturated alcohol (hereinafter referred to as “alcohol (hereinafter referred to as“ alcohol And 1) to 30% by mass, and an α, β-unsaturated aldehyde represented by the general formula (2) (hereinafter sometimes referred to as “aldehyde (2)”). It is characterized in that it contains 50 to 97% by mass.
The treating agent of the present invention is used when mining crude oil or natural gas, and is preferably used as a fluid treating agent for treating a fluid. As the fluid, fossil fuels such as natural gas, liquefied natural gas, sour gas, crude oil, naphtha, heavy aromatic naphtha, gasoline, kerosene, diesel oil, light oil, heavy oil, FCC slurry, asphalt, oil field concentrate and refined petroleum Examples include liquids or gases such as hydrocarbons such as products. Then, the treating agent of the present invention removes sulfur-containing compounds such as hydrogen sulfide contained in the fluid, removes iron sulfide generated by corrosion of iron by hydrogen sulfide and the like, and further, biocorrosion of metal. It is possible to kill the inducing microorganism.

In particular, the treating agent of the present invention has the advantages of extremely low toxicity, high thermal stability and high pH stability, as compared to conventional iron sulfide and hydrogen sulfide removing agents and disinfectants containing acrolein. The reason for this is not necessarily clear, but contributes to the higher stability due to the presence of alcohol (1), while aldehyde (2) has a hydrocarbon group such as at least one alkyl group in the β position, One of the factors is considered to be that the addition reaction of bulky molecules such as biomolecules and live long chains to the β-position is less likely to occur compared to acrolein having no substituent at the β-position.
On the other hand, with regard to the removal of iron sulfide and sulfur-containing compounds, it combines with hydrogen sulfide in equilibrium with iron sulfide, and removal thereof promotes dissolution of iron sulfide, resulting in removal of iron sulfide Although it is thought that even if it has a substituent at the β-position, the attack from generally small molecules, hydrogen sulfide and sulfur-containing compounds, is not significantly inhibited and iron sulfide removal performance is maintained. Be

[Alcohol (1)]
R ¹ to R ⁴ in the general formula (1) representing alcohol (1) 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 6 to 6 carbon atoms 12 represents an aryl group. However, R ¹ and R ³ or R ² and R ⁴ may be linked to each other to form an alkylene group having 2 to 6 carbon atoms.
The alkyl group having 1 to 10 carbon atoms which each of R ¹ to R ⁴ independently represents, may be linear, branched or cyclic, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-butyl group. Groups, 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 more preferable.
The alkenyl group having 2 to 10 carbon atoms, represented by R ¹ to R ⁴ independently, may be linear, branched or cyclic, and examples thereof include a vinyl group, an allyl group, a 2-buten-1-yl group, and 3-methyl. -2-buten-1-yl group, 1-penten-1-yl group, 1-hexen-1-yl group, 1-octen-1-yl group, 1-decene-1-yl group and the like.
Examples of the aryl group having 6 to 12 carbon atoms represented by R ¹ to R ⁴ 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.
When R ¹ and R ³ or R ² and R ⁴ are linked to each other 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, n -Pentylene group, n-hexylene group, 2-methyl-n-propylene group, 2-methyl-n-butylene group and the like.

As the alcohol (1), for example, 3-buten-1-ol, 3-penten-1-ol, 3-hexen-1-ol, 3-hepten-1-ol, 3-octene-1-ol, 3- Nonen-1-ol, 3-decene-1-ol, 3-undecene-1-ol, 3-dodecene-1-ol, 3-tridecene-1-ol, 2-methyl-3-buten-1-ol, 3-Methyl-3-buten-1-ol, 2-ethyl-3-buten-1-ol, 3-ethyl-3-buten-1-ol, 2,3-dimethyl-3-buten-1-ol, 2-isopropyl-3-buten-1-ol, 3-isopropyl-3-buten-1-ol, 2-methyl-3-penten-1-ol, 3-methyl-3-penten-1-ol, 3- Methyl-3-octene-1- , 3,7-dimethyl-3-octen-1-ol, 3,5-hexadien-1-ol, 3,6-heptadien-1-ol, 3,5-octadien-1-ol, 3,6 -Octadien-1-ol, 3,7-dimethyl-3,6-octadien-1-ol, 5-methyl-2- (1-methylethenyl) -4-hexen-1-ol, 1-cyclobutene-1-ethanol 1-cyclopentene-1-ethanol, 1-cyclohexene-1-ethanol, 1-cycloheptene-1-ethanol, 1-cyclooctene-1-ethanol, 2-methyl-1-cyclopentene-1-ethanol, 2-methyl- 1-cyclohexene-1-ethanol, 2,6,6-trimethyl-2-cyclohexene-1-methanol, 2-cyclobutene-1-meta , 2-cyclopentene-1-methanol, 2-cyclohexene-1-methanol, 2-cyclooctene-1-methanol, 2-methyl-2-cyclohexene-1-methanol, 3-methyl-2-cyclohexene-1- Methanol, 3-phenyl-3-buten-1-ol, 4-phenyl-3-buten-1-ol, 3- (o-tolyl) -3-buten-1-ol and the like can be mentioned.
Among the above, 3-buten-1-ol, 3-penten-1-ol, 3-hexen-1-ol, 3-hepten-1-ol, 3-octen-1-ol, 2-methyl-3- Buten-1-ol, 3-methyl-3-buten-1-ol, 3,7-dimethyl-3-octen-1-ol, 3,7-dimethyl-3,6-octadien-1-ol are preferred, More preferred are 3-buten-1-ol, 2-methyl-3-buten-1-ol and 3-methyl-3-buten-1-ol. These may be used alone or in combination of two or more.
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.

The alcohol (1) may be a commercially available product, or may be synthesized, for example, by the reaction of an α-olefin and formalin (see, for example, JP-A-7-285899).

[Aldehyde (2)]
R ⁵ and R ⁶ in the general formula (2) representing aldehyde (2) each independently represent an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an aryl having 6 to 12 carbon atoms Represents a group. R ⁷ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. However, R ⁵ and R ⁶ or R ⁵ and R ⁷ may be linked to each other to form an alkylene group having 2 to 6 carbon atoms.
Examples of the alkyl group having 1 to 10 carbon atoms represented by R ⁵ and R ⁶ independently include the same as the examples of the alkyl group having 1 to 10 carbon atoms represented by R ¹ to R ⁴ . 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 more preferable from the viewpoint of promoting iron sulfide removal performance and reaction with a sulfur-containing compound Is more preferred.
Examples of the alkenyl group having 2 to 10 carbon atoms represented by R ⁵ and R ⁶ independently include the same ones as exemplified for the alkenyl group having 2 to 10 carbon atoms represented by R ¹ to R ⁴ . Among them, alkenyl groups having 2 to 8 carbon atoms are preferable, and alkenyl groups having 2 to 6 carbon atoms are more preferable.
Examples of the aryl group having 6 to 12 carbon atoms represented by R ⁵ and R ⁶ independently are the same as the examples of the aryl group having 6 to 12 carbon atoms represented by R ¹ to R ⁴ . Among them, aryl groups having 6 to 10 carbon atoms are preferable.
When R ⁵ and R ⁶ are linked to each other 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, n-pentylene group, and n- Hexylene, 2-methylethylene, 1,2-dimethylethylene, 2-methyl-n-propylene, 2,2-dimethyl-n-propylene, 3-methyl-n-pentylene and the like. .
R ⁵ and R ⁶ are preferably each independently an alkyl group having 1 to 5 carbon atoms, from the viewpoint of promoting iron sulfide removal performance and reaction with a sulfur-containing compound, and also from the viewpoint of bactericidal properties. ⁵ and more preferably at least one of R ⁶ is a methyl group, more preferably R ⁵ and R ⁶ are both methyl groups.

The alkyl group having 1 to 5 carbon atoms represented by R ⁷ is, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, cyclopentyl group, etc. Can be mentioned.
When R ⁵ and R ⁷ are linked to each other to represent an alkylene group having 2 to 6 carbon atoms, examples of the alkylene group include ethylene, n-propylene, n-butylene, n-pentylene, n- Hexylene, 2-methylethylene, 1,2-dimethylethylene, 2-methyl-n-propylene, 2,2-dimethyl-n-propylene, 3-methyl-n-pentylene and the like. .
From the viewpoint of promoting iron sulfide removal performance and reaction with a sulfur-containing compound, and from the viewpoint of sterilization, it is most preferable that R ^{7 be} a hydrogen atom.

As the aldehyde (2), for example, 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-heptene 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-isobutyl-3-methyl-2-butenal, 3-methyl-2-pentyl-2-pentenal, 2,3-diethyl-2-heptenal, 2- (1,1-dimethyl) Propyl) -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-Methylcyclohexylidene) propanal, 2-cyclohexylidenebutanal, 2-cyclohexylidenehexanal, 1-cyclopropyl-2-formylcyclobutene, 1-formyl-2-methylcyclopentene, 1-formyl -5-isopropyl-2-methylcyclopentene, 1-formyl-2,5,5-trimethylcyclopentene, 1-formyl-2-methylcyclohexene, 1-formyl-2,5,6,6-tetramethylcyclohexene, 1-formyl -2,4,6,6-Tetramethylcyclohexene, 3-methyl-2,4-pentadienal, 3-methyl-2,4-hexadienal, 3-methyl-2,5-hexadienal, 3 , 5-Dimethyl-2,4-hexadienal, 3-methyl-2,4-heptadienal, 3 -Methyl-2,4-octadienal, 3-methyl-2,7-octadienal, 3,7-dimethyl-2,6-octadienal (citral), 3-methyl-2,4,6- Octatrienal, 3,7-dimethyl-2,4,6-octatrienal, 3,8-dimethyl-2,7-nonadienal, 3-methyl-2,4-decadienal, 3-methyl-2,4- Undecadienal, 3-Methyl-2,4-dodecadienal, 3-Methyl-2,4-tridecadienal, 3-phenylbutenal, 3- (o-tolyl) butenal, 3- (p-tolyl A) butenal, 3-naphthyl butenal and the like.
Among the above, 3-methyl-2-butenal, 3-methyl-2-pentenal, 3-methyl-2-hexenal, 3-methyl-2-heptenal, 3-methyl-2-octenal, 3,7-dimethyl- Preferred is 2,6-octadienal (citral), 3-ethyl-2-pentenal, 3-ethyl-2-hexenal, 3-propyl-2-hexenal, 3-methyl-2-butenal, 3-methyl-2 -Pentenal and 3-ethyl-2-pentenal are more preferable, and 3-methyl-2-butenal (senecioaldehyde, hereinafter sometimes simply referred to as "SAL") is more preferable. These may be used alone or in combination of two or more.

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.

Aldehyde (2) 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).

[Content ratio]
The treating agent of the present invention contains the above-mentioned alcohol (1) and aldehyde (2) as active ingredients, contains 1 to 30% by mass of alcohol (1) and 50 to 97% by mass of aldehyde (2).
Furthermore, although the content ratio of alcohol (1) and aldehyde (2) can also be suitably set according to the usage aspect mentioned later, alcohol (1) becomes like this. Preferably 1-20 mass%, More preferably, it is 1-10 The amount of the aldehyde (2) is preferably 60 to 97% by mass, more preferably 70 to 97% by mass.

The treatment agent of the present invention includes, in addition to alcohol (1) and aldehyde (2), β, γ-unsaturated alcohol, β, γ-unsaturated aldehyde, saturated alcohol, α, β-unsaturated carboxylic acid. In the range which does not impair the effect of
The content of the β, γ-unsaturated alcohol, β, γ-unsaturated aldehyde, saturated alcohol, and α, β-unsaturated carboxylic acid is preferably 50% by mass from the viewpoint of not impairing the effects of the present invention. % Or less, more preferably 30% by mass or less, further preferably 10% by mass, still more preferably 5% by mass or less, and may be 0% by mass.

[Optional ingredient]
The treatment agent of the present invention is a surfactant, a corrosion inhibitor, an oxygen scavenger, an iron control agent, a crosslinking agent, a breaker, a coagulant, a temperature stabilizer, a pH adjuster, dehydration adjustment, as long as the effects of the present invention are not impaired. It may further contain other ingredients such as anti-swelling agents, anti-scaling agents, biocides, friction reducers, antifoaming agents, anti-smudging agents, lubricants, clay dispersants, weighting agents, gelling agents, etc. .

In addition, the treatment agent of the present invention is dissolved in 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. You may use it as it is.

[Production method]
The method for producing the treatment agent of the present invention is not particularly limited. For example, the mixture of alcohol (1) and aldehyde (2), the other components and solvents described above, and other iron sulfides to be described later according to the use mode It can manufacture by adding and mixing an agent, a sulfur-containing compound removal agent, and a germicide.
The treatment agent of the present invention is preferably in a liquid state, but depending on the form used to remove iron sulfide and a sulfur-containing compound, a carrier etc. may be suitably supported to form a solid such as powder or granules. Good.

[Use mode]
(Removal of iron sulfide)
The treatment agent of the present invention can safely and efficiently remove iron sulfide and can be used for iron sulfide removal.
When iron sulfide is removed using the treatment agent of the present invention, the treatment agent of the present invention may be acrolein, tetrakis (hydroxymethyl) phosphine, or other iron sulfide remover such as corresponding phosphonium salt, hydrochloric acid, formic acid, etc. In the range which does not impair the effect of the present invention.

As an example of a preferred embodiment for removing iron sulfide of the present invention, a sufficient amount of the treating agent of the present invention for removing iron sulfide is added to a liquid containing iron sulfide, and the treating agent is contacted with iron sulfide It can carry out by the method of removing iron sulfide.
In the method of removing iron sulfide using the treating agent of the present invention, the amount of aldehyde (2) contained in the treating agent of the present invention is preferably 0.1 to 100 parts by mass with respect to 1 part by mass of iron sulfide. The treatment agent is added to iron sulfide and brought into contact so as to be in parts by mass, more preferably 2 to 100 parts by mass.
The temperature at which the treatment agent of the present invention is brought into contact with a liquid containing iron sulfide and treated is preferably -30 ° C to 150 ° C, more preferably 0 ° C to 130 ° C.

(Removal of sulfur-containing compounds)
The treating agent of the present invention can be used as a treating agent for removing sulfur-containing compounds in liquid or gas.
Examples of the liquid or gas include water and hydrocarbons. The hydrocarbon may be gaseous, liquid or a mixture thereof.
As the above-mentioned hydrocarbon, typically, natural gas, liquefied natural gas, sour gas, crude oil, naphtha, heavy aromatic naphtha, gasoline, kerosene, diesel oil, light oil, heavy oil, FCC slurry, asphalt, oil field concentrate, etc. These include fossil fuels and refined petroleum products. The liquid or gas may be at least one selected from the group of the above examples, and any combination of these may be employed.

The sulfur-containing compound which can be contained in the liquid or gas to be removed using the treatment agent of the present invention in the method of removing the sulfur-containing compound of the present invention is hydrogen sulfide, a compound containing —SH group or these A mixture of Here, as a compound containing a —SH group, a sulfur-containing compound represented by a chemical formula “R—SH” and classified as a mercaptan, such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, isopropyl mercaptan wherein R is an alkyl group , N-butyl mercaptan, isobutyl mercaptan, sec-butyl mercaptan, tert-butyl mercaptan, n-amyl mercaptan; phenyl mercaptan in which R is an aryl group; benzyl mercaptan in which R is an aralkyl group; It is not limited.
In the present invention, to "remove" also the reduction of the initial amount of the sulfur-containing compound in the liquid or gas, such as by converting the sulfur-containing compound present in the liquid or gas into another compound. Shall be included. The converted product after being converted into another compound may remain in the system or may be separated out of the system.

When the sulfur-containing compound in liquid or gas is removed using the treating agent of the present invention, the treating agent of the present invention comprises acrolein, formaldehyde, glyoxal, glutaraldehyde, 3-methylglutaraldehyde, 1,9-nonanedial, 2 Other sulfur-containing compound removers such as -methyl-1,8-octanedial may be added as appropriate as long as the effects of the present invention are not impaired.

As a method of removing the sulfur-containing compound of the present invention (hydrogen sulfide, a compound containing a —SH group or a mixture thereof), the treatment agent of the present invention is brought into contact with a liquid or gas to The sulfur compound may be removed.
As an example of a preferred embodiment of the method for removing sulfur-containing compounds, a method of adding an amount of the treating agent of the present invention to a liquid or gas sufficient for removing sulfur-containing compounds, a container filled with the treating agent of the present invention On the other hand, a method of circulating gaseous hydrocarbons containing these sulfur-containing compounds, a method of spraying the treatment agent of the present invention into a gas containing sulfur-containing compounds, and the like, and the like can be mentioned.

In the method of removing sulfur-containing compounds in liquid or gas using the treating agent of the present invention, the amount of aldehyde (2) contained in the treating agent of the present invention is 1 mass of sulfur-containing compound in liquid or gas The treatment agent is added to the liquid or gas and brought into contact so as to be preferably 0.1 to 100 parts by mass, more preferably 2 to 100 parts by mass with respect to parts.
In the above-described method of circulating gaseous hydrocarbon in a container filled with the treating agent of the present invention, aldehyde is added to 1 part by mass of the sulfur-containing compound in the hydrocarbon to be circulated. The addition amount of the processing agent of the present invention may be adjusted so that the amount of (2) falls within the above range.
The temperature at which the treatment agent of the present invention is brought into contact with the liquid or gas added and brought into contact with it is preferably in the range of -30 ° C to 150 ° C, more preferably 0 ° C to 130 ° C.

In the case of removing a sulfur-containing compound in liquid or gas using the treating agent of the present invention, if the object to be treated is a liquid, the storage tank, the pipeline for transport, the distillation column for purification It can add by well-known means, such as injection | pouring etc. When the object to be treated is a gas, the treatment agent of the present invention may be placed in contact with the gas, or the gas may be passed through an absorption tower filled with the treatment agent of the present invention. it can.

In addition, in the method of removing sulfur-containing compounds in liquid or gas using the treatment agent of the present invention, nitrogen-containing compounds are further added to the extent that the effect of the present invention is further enhanced or not impaired. It is also good.
Examples of the nitrogen-containing compounds include N, N′-oxybis (methylene) bis (N, N-dibutylamine) and N, N ′-(methylene bis (oxy) bis (methylene)) bis (N, N-dibutylamine) ), 4,4′-oxybis (methylene) dimorpholine, bis (morpholinomethoxy) methane, 1,1′-oxybis (methylene) dipiperidine, bis (piperidinomethoxy) methane, N, N′-oxybis (methylene) bis (N, N-dipropylamine), N, N '-(methylenebis (oxy) bis (methylene)) bis (N, N-dipropylamine), 1,1'-oxybis (methylene) dipyrrolidine, bis (pylori) Dinomethoxy) methane, N, N′-oxybis (methylene) bis (N, N-diethylamine), N, N ′-(methylene bis (oxy) bis (meth) ene (L)) α-Aminoether compounds such as bis (N, N-diethylamine); 1,3,5-trimethoxypropyl-hexahydro-1,3,5-triazine, 1,3,5-trimethoxyethyl-hexahydro- 1,3,5-triazine, 1,3,5-tri (3-ethoxypropyl) -hexahydro-1,3,5-triazine, 1,3,5-tri (3-isopropoxypropyl) -hexahydro-1 , 3,5-triazine, 1,3,5-tri (3-butoxypropyl) -hexahydro-1,3,5-triazine, 1,3,5-tri (5-methoxypentyl) -hexahydro-1,3 Alkoxy-hexahydrotriazine compounds such as 1,5-triazine; 1,3,5-trimethyl-hexahydro-1,3,5-triazine, 1,3,5-triethyl Alkyl such as -hexahydro-1,3,5-triazine, 1,3,5-tripropyl-hexahydro-1,3,5-triazine, 1,3,5-tributyl-hexahydro-1,3,5-triazine -Hexahydrotriazine compounds; 1,3,5-tri (hydroxymethyl) -hexahydro-1,3,5-triazine, 1,3,5-tri (2-hydroxyethyl) -hexahydro-1,3,5- Hydroxyalkyl-hexahydrotriazine compounds such as triazine, 1,3,5-tri (3-hydroxypropyl) -hexahydro-1,3,5-triazine; monomethylamine, monoethylamine, dimethylamine, dipropylamine, trimethylamine, Triethylamine, tripropylamine, monomethanol amine, dimethanol amine , Trimethanol amine, diethanolamine, triethanolamine, monoisopropanolamine, dipropanolamine, diisopropanolamine, tripropanolamine, N-methylethanolamine, dimethyl (ethanol) amine, methyldiethanolamine, dimethylaminoethanol, ethoxyethoxyethanol tert Monoamine compounds such as -butylamine; aminomethylcyclopentylamine, 1,2-cyclohexanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, bis (tert-butylaminoethoxy) ethane and the like Imine compounds; imidazoline compounds; hydroxyamino alkyl ether compounds; morpholine compounds; pyrrolidone compounds Piperidine compound; alkylpyridine compound; 1H-hexahydroazepine; reaction product of alkylenepolyamine and formaldehyde such as reaction product of ethylenediamine and formaldehyde; polyvalent metal chelate compound of aminocarboxylic acid; benzyl (cocoalkyl) (cocoalkyl) Dimethyl) quaternary ammonium chloride, di (coco alkyl) dimethyl ammonium chloride, di (tallow alkyl) dimethyl quaternary ammonium chloride, di (hydrogenated tallow alkyl) dimethyl quaternary ammonium chloride, dimethyl (2-ethylhexyl) (tallow alkyl) Quaternary ammonium salt compounds such as ammonium methyl sulfate, (hydrogenated tallow alkyl) (2-ethylhexyl) dimethyl quaternary ammonium methyl sulfate Polyethyleneimine, polyallylamine, polyvinylamine; aminocarbinol compound; aminal compound; bisoxazolidine compound; and the like. These may be used alone or in combination of two or more.
In addition, when these nitrogen-containing compounds are added to hydrocarbons, NOx (Knox) is generated in purification, and there is a concern about the load on the environmental impact. In consideration of this, it is more preferable not to add the nitrogen-containing compound.

(Control of biological corrosion of metals)
The treatment agent of the present invention can be used for the control of metal biocorrosion because it can kill microorganisms that induce metal biocorrosion. That is, the treating agent of the present invention can be used as a biocorrosion inhibitor for suppressing biocorrosion of metal.
When the treatment agent of the present invention is used as a biocorrosion inhibitor, it may further contain conventional ingredients in the field of germicide, as long as the object of the present invention is not impaired. As the components, for example, other bactericidal agents, antibacterial agents, dispersing agents, suspending agents, spreading agents, penetrants, wetting agents, caking agents, stabilizers, flame retardants, coloring agents, antioxidants, antistatic agents Agents, foaming agents, lubricants, gelling agents, coalescent agents, antifreeze agents, viscosity modifiers, pH adjusters, preservatives, emulsifiers, antifoam agents, carriers and the like.

Examples of the above-mentioned other bactericidal agents include oxidizing agents (peracetic acid, potassium monopersulfate, sodium perborate, hydrogen peroxide, sodium percarbonate etc.), phosphonium salts (THPS, polyether polyamino methylene phosphonate, tributyl tetradecyl phosphonium) Chloride, etc., alkyl benzene sulfonic acid, quaternary ammonium salt (N-alkyl dimethyl benzyl ammonium chloride, N-dialkyl methyl benzyl ammonium chloride etc.), isothiazoline, thiazoline, isothiazolone compound (2- (thiocyanomethylthio) benzothiazole, isothiazolone Etc.), thiocarbamate compounds, hydroquinone compounds, aldehyde compounds other than aldehyde (2) (glutaraldehyde, chloroacetaldehyde, 1,9-nonanedi) (2-methyl-1, 8-octanedial, 3-methylglutaraldehyde etc.), azo compounds, benzalkonium chloride, hypochlorous acid, oxazolidine compounds, imidazole compounds (1,2-dimethyl 5-nitro-1H-imidazole etc.), aminoalcohols, ethers, liposomes, alkyne alkoxylates, brominated biocides (eg 2,2-dibromo-2-nitroacetamide), enzymes (endo-β-) 1,2-galactanase etc.), metal ions, phenolic compounds and the like. These germicides may be used alone or in combination of two or more.

Examples of the dispersant include sulfuric acid esters of higher alcohols, alkyl sulfonic acids, alkyl aryl sulfonic acids, oxyalkyl amines, fatty acid esters, polyalkylene oxide-based surfactants, anhydrosorbitol-based surfactants, etc .; soaps, casein, gelatin And starch, alginic acid, agar, carboxymethylcellulose (CMC), polyvinyl alcohol, pine oil, soy sauce, bentonite, cresol soap and the like. These dispersants may be used alone or in combination of two or more.

Examples of the carrier include water, alcohol (methanol, ethanol, isopropanol, glycol, glycerin, etc.), ketone (acetone, methyl ethyl ketone, etc.), aliphatic hydrocarbon (hexane, liquid paraffin, etc.), aromatic hydrocarbon (benzene, xylene, etc.) Liquid carriers such as halogenated hydrocarbons, acid amides, esters and nitriles; Clays (kaolin, bentonite, acid clay etc), talcs (talcose powder, wax powder etc), silicas (diatomaceous earth, anhydrous silica) , Mica powder, alumina, sulfur powder, activated carbon, etc .; These carriers may be used alone or in combination of two or more.

Aldehyde (2) which is an active ingredient of the processing agent of the present invention has a bactericidal action on microorganisms.
There are no particular restrictions on the microorganism to which the treatment agent of the present invention is applied as a biocorrosion inhibitor, and there are no particular limitations, and Escherichia coli, Shigella, Salmonella, Legionella, Vibrio, Staphylococcus, Streptococcus, Enterococcus, Bacillus anthracis, Microorganisms found in normal living environment such as botulinum and tetanus bacteria, Microorganisms causing biocorrosion of metal such as sulfate reducing bacteria, nitrate reducing bacteria, methanogenic bacteria, iodine oxidizing bacteria, iron oxidizing bacteria and sulfur oxidizing bacteria Can be mentioned.
Since the aldehyde (2) is characterized by low toxicity, high thermal stability and high pH stability, the treatment agent of the present invention is suitably used to inhibit biocorrosion of metals. In the present invention, the term "suppression" of biocorrosion is a concept including preventing the occurrence of biocorrosion and suppressing the progress (deterioration) of biocorrosion.

The above "sulfate reducing bacteria" is a generic term for microorganisms having the ability to reduce sulfate. Specific examples of the sulfate reducing bacteria include microorganisms of the genus Desulfovibrio, microorganisms of the genus Desulfobacter, and microorganisms of the genus Desulfotomaculum.

The "nitrate reducing bacteria" is a generic term for microorganisms having the ability to reduce nitrate.

The above-mentioned "methane-producing bacteria" is a generic term for microorganisms having the ability to produce methane under an anaerobic environment. Specific examples of the methanogen include a microorganism of the genus Methanobacterium, a microorganism of the genus Methanococcus, a microorganism of the genus Methanosarcina, and the like.

The “iodine-oxidizing bacteria” is a general term for microorganisms having the ability to oxidize iodide ion (I ⁻ ) to molecular iodine (I ₂ ). Specific examples of the iodine-oxidizing bacteria include Roseovarius sp. 2S-5, Iodide oxidizing bacteria strain MAT3 and the like.

The “iron-oxidizing bacteria” is a general term for microorganisms having the ability to oxidize divalent iron ions (Fe ²⁺ ) to trivalent iron ions (Fe ³⁺ ). Specific examples of iron-oxidizing bacteria include Mariprofundus ferrooxydans, Acidithiobacillus ferrooxidans and the like.

The "sulfur oxidizing bacteria" is a general term for microorganisms having the ability to oxidize sulfur or inorganic sulfur compounds. Specific examples of sulfur-oxidizing bacteria include Thiobacillus bacteria, Acidithiobacillus bacteria, Sulfolobus archaea, Acidianus archaea and the like.

When the treatment agent of the present invention is used as a metal biocorrosion inhibitor, at least one selected from sulfate reducing bacteria, nitrate reducing bacteria, methanogenic bacteria, iodine oxidizing bacteria, iron oxidizing bacteria and sulfur oxidizing bacteria; more preferably sulfuric acid At least one member selected from reducing bacteria, nitrate reducing bacteria and methanogens; more preferably at least one member selected from sulfuric acid reducing bacteria and methanogens; particularly preferably used to inhibit biocorrosion by methanogens Is preferred.

Methanogens prefer an anaerobic environment, and inhabit paddy fields and even swamps, ponds, lakes, rivers, oceans and mining sites for fossil fuels.
Sulfate reducing bacteria prefer an anaerobic environment and inhabit most environments that contain water, such as forest soil, fields, marshes, ponds, lakes, rivers and the sea.
Nitrate reducing bacteria prefer an anaerobic environment and can grow in an oxidizing environment as compared to methanogenic bacteria and sulfate reducing bacteria, so they live in the above environment.
Iron-oxidizing bacteria are present in mining wastewater and the like. It also inhabits places where sediments of a little brown are accumulated in rivers etc.
Sulfur-oxidizing bacteria inhabit the same environment as iron-oxidizing bacteria and also in domestic wastewater, so they are also involved in concrete corrosion of sewage pipes. It also inhabits the hot springs that contain sulfur.
The location where relatively many iodine oxidation bacteria exist is underground irrigation, and also exists widely in the marine environment.
Therefore, when the treatment agent of the present invention is used as a metal biocorrosion inhibitor, it is suitably used to suppress the biocorrosion of metal present or placed in the above-mentioned microorganism habitat.

When the treatment agent of the present invention is used as a metal biocorrosion inhibitor, the metal to be treated is not particularly limited as long as it is exposed to the environment where a microorganism causing biocorrosion is present, for example, iron, copper, zinc , Tin, aluminum, magnesium, titanium, nickel, chromium, manganese, molybdenum, and alloys containing at least one selected from these. Among them, from the viewpoint of industrial use, iron and an alloy containing iron are preferable, and iron is more preferable.

There is no particular limitation on the method of use when using the treatment agent of the present invention as a metal biocorrosion inhibitor, but in one aspect, for example, when the metal is exposed to an environment where microorganisms causing biocorrosion are present The method etc. of making the processing agent of this invention exist in the said environment beforehand are mentioned. To cite a specific example of this aspect, in the mining of fossil fuels (for example, petroleum, natural gas, shale oil, shale gas, etc.) by the hydraulic fracturing method, the present invention is applied to a liquid (high pressure water) injected at high pressure into rock etc. By adding and dissolving the treatment agent in advance, it is possible to suppress biocorrosion that occurs in metals (for example, metal pipes that are flow channels of high pressure water) with which high pressure water comes in contact. In another embodiment, for example, a method of applying or spraying the treatment agent of the present invention as it is or a solution in which water or an organic solvent is dissolved or dispersed is applied to the surface of a metal required to inhibit biocorrosion. Etc.

As a use form in the case of using the processing agent of this invention as a metal biocorrosion inhibitor, it is preferable that it is an aqueous or oily solution form in which the total concentration of the above-mentioned active ingredient aldehyde (2) is within a specific range. .

The total concentration of aldehyde (2) which is the active ingredient in such a solution is usually 10000 ppm or less, preferably 0.01 ppm to 3000 ppm, more preferably 0.1 ppm to 1000 ppm from the viewpoint of cost effectiveness. When the concentration is 0.01 ppm or more, the bactericidal effect is easily exhibited, and when it is 10000 ppm or less, it does not become a large excess and it is easy to use in price. In the present specification, "ppm" means "mass ppm" unless otherwise specified.

The method for producing the solution is not particularly limited, and a method known per se or a method analogous thereto can be used. For example, it can be produced by adding the above-mentioned active ingredient aldehyde (2) to a suitable liquid carrier, stirring, dissolving or dispersing it. As the said liquid carrier, the liquid carrier etc. which were illustrated above as one of the components which the processing agent of this invention may contain, for example are mentioned.

The solution is available, for example, mixed with high pressure water used in hydraulic fracturing. When the solution is used in combination with the high pressure water, the solution may contain conventional components (eg, proppant, viscosity modifier, surfactant, acid, etc.) in high pressure water.
The solution may also be applied or sprayed to the surface of the metal for which the inhibition of biocorrosion is required.

When the treatment agent of the present invention is used, a sterilization method known per se or a method analogous thereto may be used in combination as long as the object of the present invention is not impaired.
For example, known antibacterial agents may be used in combination, or a sterilization method by pH control (see, for example, WO 2010/056114, WO 2008/143778) or a sterilization method by ultrasonic irradiation (for example, international) See, for example, Publication No. 2000/024679, etc.) may be used in combination. Examples of known germicides that can be used in combination with the treatment agent of the present invention include the other germicides exemplified above as one of the components that may be contained in the treatment agent of the present invention.

Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to these, and unless otherwise specified, "%" means "% by mass".

The treatment agents and acrolein used in the examples and comparative examples are as follows.
Treatment agent 1:
The compound synthesized from 3-methyl-2-buten-1-ol is purified and distilled according to the method described in JP-A No. 60-224652 (SAL: 94.6% by mass, 3-methyl-3) -Buten-1-ol: 3.6% by mass, 3-methyl-3-butenal: 1.2% by mass, 3-methyl-2-buten-1-ol: 0.3% by mass, 3-methyl-1 -Butanol: contains 0.1% by mass, 3-methylcrotonic acid: 0.2% by mass.)
Treatment agent 2:
A mixture of 3-methyl-2-buten-1-ol added to treating agent 1 (SAL: 88.4% by mass, 3-methyl-3-buten-1-ol: 9.9% by mass, 3-methyl -3-butenal: 1.1% by mass, 3-methyl-2-buten-1-ol: 0.3% by mass, 3-methyl-1-butanol: 0.1% by mass, 3-methylcrotonic acid: 0 .2% by mass is contained.)
Acrolein:
Made by Tokyo Chemical Industry Co., Ltd., containing hydroquinone as a stabilizer

[Iron sulfide removal test]
<Example 1> (Treatment agent 1)
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 138.2 mg (0.5 mmol) was added, and upon stirring, iron sulfide was formed as a fine black precipitate. 134.5 mg (1.5 mmol as SAL) of treatment agent 1 were added thereto, and the reaction solution was heated to 50 ° C. while being stirred at 500 rpm. The state of iron sulfide was observed after 0 hours, at which time treatment agent 1 was added. As a result, iron sulfide was dissolved after 6 hours, and the reaction solution became colorless and transparent.

<Example 2> (Treatment agent 2)
The same test as in Example 1 was carried out except that treatment agent 2 was used instead of treatment agent 1 and the amount used was changed from 134.5 mg to 288.5 mg (3.0 mmol as SAL). After 8 hours, the iron sulfide dissolved and the reaction solution became colorless and transparent.

Comparative Example 1 Acrolein
The same test as in Example 1 was conducted except that acrolein was used instead of treating agent 1. After 4 hours, the iron sulfide dissolved and the reaction solution became colorless and transparent.

[Hydrogen sulfide removal test]
<Example 3> (Treatment agent 1)
20 g of kerosene (manufactured by Wako Pure Chemical Industries, Ltd.) is added to a 50 mL three-necked flask, and a mixed gas consisting of 1 volume% hydrogen sulfide and 99 volume% nitrogen is circulated at a flow rate of 50 mL / min and stirred at 800 rpm The gas in the three-necked flask was replaced. After 2 hours, the flow of the mixed gas was stopped, and the three-necked flask was sealed, and the hydrogen sulfide concentration in the gas phase in the three-necked flask was measured with a Kitagawa-type gas detection tube and was 8500 ppm by volume. Next, 1.5 g (16.9 mmol as SAL) of Treatment Agent 1 was added, and then the inside of the apparatus was reacted at room temperature for 5 hours while being stirred at 800 rpm. After the reaction, the concentration of hydrogen sulfide in the gas phase in the three-necked flask was measured to be 5,300 ppm by volume, and the removal rate was 38%.

<Example 4> (Treatment agent 2)
The same test as in Example 3 was carried out except that treatment agent 2 was used instead of treatment agent 1. It was 5500 volume ppm when the hydrogen sulfide concentration of the gaseous-phase part in a three-necked flask after reaction was measured, and the removal rate was 35%.

Comparative Example 2 Acrolein
The same test as in Example 3 was conducted except that acrolein was used instead of treating agent 1. After the reaction, the concentration of hydrogen sulfide in the gas phase in the three-necked flask was measured to be 5,300 ppm by volume, and the removal rate was 38%.

[Thermal stability test]
<Test Example 1> Thermal stability test The treating agent 1 and acrolein were placed in a 50 mL three-necked flask, heated to 50 ° C. under a nitrogen atmosphere, and the content of SAL and acrolein immediately after the temperature increase was 100%. The change in content was observed by a calibration curve method by gas chromatography using an internal standard. The results are shown in Table 1.

[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)

After 10 hours, 100.0% of SAL in Treatment 1 remained, whereas 3.4% was lost despite the fact that acrolein contained hydroquinone as a stabilizer. From this result, it can be understood that SAL in the treatment agent 1 has extremely high thermal stability than acrolein.

[PH stability test]
<Test Example 2> pH Stability Test The treating agent 1 and acrolein were dissolved in 0.5 mol / L phosphate buffer solutions of different pH prepared by the following method, respectively, to prepare a 0.1% solution. 50 mL of the solution is put in a sample bottle under a nitrogen atmosphere, stored at 23 ± 2 ° C., and the change with time of the content when the contents of SAL and acrolein at the time of preparation are 100% It observed by the absolute calibration method by graphic analysis. The results are shown in FIGS. 1 and 2.
From this result, it can be seen that SAL in treatment agent 1 has extremely high pH stability than acrolein.

(Preparation of phosphate buffer)
pH 1.72: 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 6.20: 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 8.13: 0.3 g of sodium dihydrogen phosphate dihydrate and 13.9 g of disodium hydrogen phosphate were dissolved in 200 mL of distilled water.

(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

<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.

From the above Examples, Comparative Examples, Test Examples and Reference Examples, the treating agent containing alcohol (1) and aldehyde (2) has iron sulfide and hydrogen sulfide removing ability equivalent to that of acrolein, and has a thermal conductivity higher than that of acrolein. It can be seen that the stability and pH stability are high and safe.

The treating agent of the present invention has an active ingredient having high thermal stability and pH stability, and is useful for removing iron sulfide and removing sulfur-containing compounds used in mining of crude oil or natural gas, and metal It is also useful as a biocorrosion inhibitor for suppressing the biocorrosion of

Claims

1 to 30% by mass of a γ, δ-unsaturated alcohol represented by the following general formula (1) and 50 to 97% by mass of an α, β-unsaturated aldehyde represented by the following general formula (2) Processing agent for crude oil or natural gas mining.

In the general formula (1), R 1 to R 4 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. However, R 1 and R 3 or R 2 and R 4 may be connected to each other to form an alkylene group having 2 to 6 carbon atoms.

In (formula (2), .R 7 represents an alkyl group, an alkenyl group or an aryl group having 6 to 12 carbon atoms having 2 to 10 carbon atoms of R 5 and R 6 are 1 to 10 carbon atoms each independently And a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, provided that R 5 and R 6 or R 5 and R 7 may be connected to each other to form an alkylene group having 2 to 6 carbon atoms.
The processing agent according to claim 1, wherein R 7 is a hydrogen atom.
The processing agent according to claim 1, which is for removing iron sulfide.
A method of contacting iron sulfide with the treating agent according to claim 3 to remove the iron sulfide.
The said processing agent is made to contact the said iron sulfide so that the (alpha), (beta)-unsaturated aldehyde in the said processing agent may be 0.1-100 mass parts with respect to 1 mass part of said iron sulfides. the method of.
The method according to claim 4 or 5, wherein the treating agent and the iron sulfide are brought into contact in the range of -30 ° C to 150 ° C.
Use of the treating agent according to claim 3 for removing iron sulfide.
The treatment according to claim 1 or 2, which is a treating agent for removing a sulfur-containing compound in liquid or gas, wherein the sulfur-containing compound is a compound containing hydrogen sulfide, -SH group or a mixture thereof. Agent.
The processing agent according to claim 8, wherein the liquid or gas is a hydrocarbon.
The liquid or gas is selected from the group consisting of natural gas, liquefied natural gas, sour gas, crude oil, naphtha, heavy aromatic naphtha, gasoline, kerosene, diesel oil, light oil, heavy oil, FCC slurry, asphalt and oil field concentrate The treatment agent according to claim 8, which is at least one.
A method of removing a sulfur-containing compound in liquid or gas, wherein the sulfur-containing compound is hydrogen sulfide, a compound containing an -SH group, or a mixture thereof, Contacting the agent with the liquid or gas.
The method according to claim 11, wherein the liquid or gas is a hydrocarbon.
The liquid or gas is selected from the group consisting of natural gas, liquefied natural gas, sour gas, crude oil, naphtha, heavy aromatic naphtha, gasoline, kerosene, diesel oil, light oil, heavy oil, FCC slurry, asphalt and oil field concentrate The method according to claim 11, wherein the method is at least one.
The treatment agent is brought into contact with the liquid or gas such that the α, β-unsaturated aldehyde contained in the treatment agent is 0.1 to 100 parts by mass with respect to 1 part by mass of the sulfur-containing compound. Item 14. The method according to any one of Items 11 to 13.
The method according to any one of claims 11 to 14, wherein the treating agent and the liquid or gas are brought into contact in the range of -30 ° C to 150 ° C.
The use of the treating agent according to any one of claims 8 to 10 for removing a sulfur-containing compound which is a liquid or gas containing hydrogen sulfide, a -SH group-containing compound or a mixture thereof.
The processing agent of Claim 1 or 2 for suppression of the biocorrosion of a metal.
A sterilizing method using the treatment agent according to claim 17.
The use of the treatment according to claim 17 as a biocorrosion inhibitor which suppresses biocorrosion of metals.