TW201816098A - Composition for removing iron sulfide - Google Patents

Abstract

Provided is a composition for removing iron sulfide, the composition containing an [alpha], [beta]-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

   Composition for removing iron sulfide   

The present invention relates to a composition for removing iron sulfide and a method for removing iron sulfide using the same.

Fossil fuels or refined petroleum products such as natural gas, liquefied natural gas, sour gas, crude oil, petroleum brain, heavy aromatic petroleum brain, gasoline, kerosene, diesel, light oil, heavy oil, FCC slurry, asphalt, oil field concentrates, etc. Hydrogen sulfide, which is often present in hydrocarbons, corrodes iron used in excavation equipment, etc., and causes iron sulfide. Iron sulfide accumulates as deposits in the manufacturing facilities of fossil fuels or refined petroleum products, reducing the operating efficiency of machinery such as heat exchangers, cooling towers, reaction vessels, pipelines, or furnaces, or preventing the use of equipment for equipment maintenance. Correct measurement, so it is best to remove it.

As a method for removing iron sulfide, a method of using acrolein to melt iron sulfide is known. In the SPE Annual Technical Conference and Exhibition SPE 146080 held in Denver, Colorado, USA from October 30, 2011 to November 2, 2011, The removal of iron sulfide using acrolein as an active ingredient has also been published. However, acrolein is a highly toxic compound whose concentration is strictly regulated in terms of labor safety and environmental safety, and there are problems that require attention in handling. In addition, acrolein is extremely easy to polymerize. In terms of lack of thermal stability, or lack of pH stability, it gradually decreases the amount of presence due to the pH of the environment in which it is used, and it also becomes a problem in handling.

Prior art literature Non-patent literature

Non-Patent Literature 1 SPE Annual Technical Conference and Exhibition SPE 146080, 2011; http://dx.doi.org/10.2118/146080-MS

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 a safer and more stable compound is desired instead. Therefore, an object of the present invention is to provide a composition having an active ingredient having high thermal stability and high pH stability, and capable of removing iron sulfide safely and efficiently.

According to the present invention, the above-mentioned objects can be achieved by the following [1] to [7].

[1] A composition for removing iron sulfide, which contains an α, β-unsaturated aldehyde (hereinafter, referred to as an aldehyde (1)) as an active ingredient represented by the following general formula (1).

(R ¹ to R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Among them, R ¹ and R ² or R ³ They are connected to each other to form an alkylene group having 2 to 6 carbon atoms, and R ¹ and R ^{2 are} not hydrogen atoms at the same time.)

[2] The composition according to [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 according to [1] or [2], wherein R ³ is a hydrogen atom.

[4] A method for removing iron sulfide, characterized in that the composition according to any one of [1] to [3] is brought into contact with iron sulfide.

[5] The method according to [4], wherein the aldehyde (1) in the composition is added to 0.1 to 100 parts by mass based on 1 part by mass of iron sulfide.

[6] The method according to [4] or [5], wherein the aldehyde (1) in the composition is brought into contact with iron sulfide in a range of -30 ° C to 150 ° C.

[7] Use of a composition according to any one of [1] to [3], which is for removing iron sulfide.

The composition of the present invention is excellent in the removal performance of iron sulfide by containing aldehyde (1).

In particular, compared with the conventional iron sulfide remover containing acrolein, the composition of the present invention has the advantages of extremely low toxicity, high thermal stability, and high pH stability. Although the reason may not be clear, since aldehyde (1) has at least one alkyl group, alkenyl group or aryl group at the β position, it is considered to be a biomolecule or a growing chain compared with acrolein having no substituent at the β position One of the main factors is that it is difficult for the large molecule to cause the addition reaction at the β position. On the other hand, regarding the removal of iron sulfide, it is thought that combining iron sulfide with hydrogen sulfide in equilibrium and removing it will promote the dissolution of iron sulfide. As a result, iron sulfide is removed. It also does not hinder the attack of hydrogen sulfide from ordinary small molecules, and the removal performance of iron sulfide is maintained.

FIG. 1 is a graph showing pH stability of butenal (SAL).

Fig. 2 is a graph showing the pH stability of acrolein.

Embodiment of the invention

The composition of the present invention is characterized by containing an aldehyde (1) as an active ingredient.

In the aldehyde (1), R ¹ to R ³ each independently represent an alkyl group having 1 to 10 carbon atoms, which may be linear, branched, or cyclic. Examples include methyl, ethyl, n-propyl, and isopropyl. Group, n-butyl, isobutyl, t-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, cyclopentyl and the like. From the viewpoint of the removal performance of iron sulfide, among them, methyl, ethyl or n-propyl is preferred, methyl or ethyl is more preferred, and methyl is more preferred.

The alkenyl group having 2 to 10 carbon atoms independently represented by R ¹ to R ³ may be linear or branched or cyclic, and examples thereof include vinyl, allyl, 1-penten-1-yl, 4- Methyl-3-penten-1-yl, 4-penten-1-yl, 1-hexen-1-yl, 1-octen-1-yl, 1-decen-1-yl, and the like. Among them, alkenyl groups having 1 to 8 carbon atoms are preferred, and alkenyl groups having 1 to 6 carbon atoms are more preferred.

R ¹ to R ³ each independently represent an aryl group having 6 to 12 carbon atoms, and examples thereof include phenyl, tolyl, ethylphenyl, xylyl, trimethylphenyl, naphthyl, and biphenyl. Among them, an aryl group having 6 to 10 carbon atoms is preferred.

In addition, when R ¹ and R ² or R ^{3 are} connected to each other to represent an alkylene group having 2 to 6 carbon atoms, examples of the alkylene group include ethylene, n-propyl, and n-butenyl. , N-pentyl, n-hexyl, 2-methylethylene, 1,2-dimethylethyl, 2-methyl-n-propyl, 2,2-dimethyl- n-propyl, 3-methyl-n-pentyl and the like.

R ¹ to R ³ are each preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

Having the iron sulfide removal performance from the standpoint of ensuring the thermal stability and pH stability of view and, based preferred R ^1, R ² is at least one of methyl, more preferably based R ^1, R ² are methyl.

From the viewpoint of promoting the reaction with hydrogen sulfide and efficiently removing iron sulfide, R ^{3 is} preferably a hydrogen atom.

Examples of the aldehyde (1) include 2-butenal, 2-pentenal, 2-hexenal, 2-heptenal, 2-octenal, 2-nonenal, and 2-decane Enal, 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-di Methyl-2-heptenal, 2,5-dimethyl-2-hexenal, 2,6-dimethyl-2-heptenal, 2,4,4-trimethyl-2-pentene Enal, 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-pentenal, 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-pentene Aldehyde, 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-butan Enal, 2-ethyl-3-methyl-2-butenal, 2-isopropyl-3-methyl-2-butene Aldehyde, 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-dimethylpropyl) -3-methyl-2- Butenal, 3,5,5-trimethyl-2-hexenal, 2,3,4-trimethyl-2-pentenal, 2-cyclopropylenepropanal, 2-cyclopentene Propanal, 2-cyclopentylidenehexanal, 2- (3-methylcyclopentylidene) propanal, 2-cyclohexylenepropanal, 2- (2-methylcyclohexylene) propanal, 2-cyclohexylenebutyraldehyde, 2-cyclohexylenehexanaldehyde, 1-methylfluorenylcyclobutene, 1-methylfluorenyl-3,3-dimethylcyclobutene, 1-cyclopropyl-2- Formamylcyclobutene, 1-formamylcyclopentene, 5-ethyl-1-formamylcyclopentene, 1-formamyl-3-methylcyclopentene, 1-formamyl- 4-methylcyclopentene, 1-methylfluorenyl-5-methylcyclopentene, 1-methylfluorenyl-3,3-dimethylcyclopentene, 1-methylfluorenyl-4,5-di Methylcyclopentene, 1-methylfluorenyl-2-methylcyclopentene, 1-methylfluorenyl-5-isopropyl-2-methylcyclopentene, 1-methylfluorenyl-2,5, 5-trimethylcyclopentene, 1-methylfluorenylcyclohexene, 1-methylfluorenyl-3-methylcyclohexene, 1-methylfluorenyl-4-methylcyclohexene, 1-methyl Methyl-5-methylcyclohexene, 1-methylfluorenyl-6-methylcyclohexene, 1-methylfluorenyl-3,3-dimethylcyclohexene, 1-methylfluorenyl-5,5 -Dimethylcyclohexene, 1-methylfluorenyl-2 methylcyclohexene, 1-methylfluorenyl-2,5,6,6-tetramethylcyclohexene, 1-methylfluorenyl-2, 4,6,6-tetramethylcyclohexene, 1-methylfluorenylcycloheptene, 1-methylfluorenyl-2-methylcycloheptene, 1-methylfluorenyl-3-methylcycloheptene, 1-methylfluorenyl cyclooctene, 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-octadial (citral), 2, 4,6-octatrienal, 7-methyl-2,4,6-octatrienal, 2,4-nonanedial, 2,6-nonedial, 4,8-dimethyl-2 , 7-nonanedialdehyde, 2,4-decanedial, 2,4-undecadienal, 2,4-dodecadienal, 2,4-tridecadienal, 2, 4,7-Thirteen carbon trienal, 3-phenyl acrolein, 3-phenyl-2-methacryl, 3- (o-tolyl) acrolein, 3- (p-tolyl) propylene Aldehyde, 3-naphthyl acrolein and the like. Among them, 3-methyl-2-butenal, 3-methyl-2-pentenal, 3-methyl-2-hexenal, 3-methyl-2-heptenal, 3 -Methyl-2-octenal, 3,7-dimethyl-2,6-octadial (citral), 3-ethyl-2-pentenal, 3-ethyl-2-hexan Enal, 3-propyl-2-hexenal, more preferably 3-methyl-2-butenal, 3-methyl-2-pentenal, 3-ethyl-2-pentenal, More preferred is 3-methyl-2-butenal (butenal, hereinafter simply referred to as SAL).

For compounds having a trans form and a cis form, either one or a mixture may be used. When a mixture is used, an arbitrary mixing ratio may be used.

The aldehyde (1) may be a commercially available product, or may be synthesized by an oxidative dehydrogenation reaction of a corresponding α, β-unsaturated alcohol (see, for example, Japanese Patent Application Laid-Open No. 60-224652).

The content ratio of the aldehyde (1) as the active ingredient in the composition of the present invention can be appropriately set according to the use situation, and is usually 1 to 99.9% by mass. From the viewpoint of cost and effect, it 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, methane (hydroxymethyl) phosphine or the corresponding sulfonium salt, hydrochloric acid, formic acid and the like within a range that does not impair the effects of the present invention.

In addition, the composition of the present invention may contain cyclohexane, toluene, xylene, heavy aromatic petroleum naphtha, petroleum distillates, methanol, ethanol, ethylene glycol, and the like having a carbon number of 1 to 10, or a diol, and the like. Appropriate solvent.

In addition to the aldehyde (1), the composition of the present invention may contain a surfactant, a preservative, a deoxidizing agent, an iron content control agent, a cross-linking agent, a breaker, and an aggregating agent as long as the effects of the present invention are not impaired 、 Temperature stabilizer, pH adjuster, dehydration adjuster, swelling preventer, antiscalant, biocide, friction reducing agent, defoamer, sludge preventer, lubricant, clay dispersant, weighting agent, gel Ingredients such as chemical agents.

The manufacturing method of the composition of this invention is not specifically limited, For example, it can manufacture by adding arbitrary components, such as the said other iron sulfide remover, a solvent, etc., to aldehyde (1).

The composition of the present invention is preferably in a liquid state, can be supported on an appropriate carrier or the like depending on the form used for removing iron sulfide, and can be a solid state such as a powder or a fluid.

As an example of a preferred embodiment of the present invention, the composition of the present invention sufficient to remove iron sulfide may be 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 100 parts by mass relative to 1 part by mass of iron sulfide, and more The best line is added to 2 ~ 100 parts by mass. The temperature at which the composition of the present invention is added to a liquid containing iron sulfide and brought into contact for processing is preferably in a range of 0 ° C to 150 ° C, and more preferably in a range of 20 ° C to 130 ° C.

Examples

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples. The SAL, citral, and acrolein used in the examples and comparative examples are as follows.

SAL: Synthesized from prenol according to the method described in Japanese Patent Laid-Open No. 60-224652 (purity 98.1%)

Citral: manufactured by Kuraray Co., Ltd. (purity 98.0%, trans: cis = 51: 49 ~ 57: 43 (molar ratio))

Acrolein: manufactured by Tokyo Chemical Industry Co., Ltd. as a stabilizer and containing hydroquinone

    <Example 1> Iron sulfide removal test (SAL)    

In a 1 L three-necked flask equipped with a thermometer, a stirrer, and a cooling tube, 500 mL of distilled water, 1 mL of 1 mol / L hydrochloric acid, and 120.0 mg (0.5 mmol) of sodium sulfide were added. 9 hydrate, 138.2 (0.5 mmol) of iron sulfate. 7 hydrate, iron sulfide is formed into fine black precipitates when stirred. 126.3 mg (1.5 mmol) of SAL was added thereto, and the reaction liquid was heated to 500C while stirring at 500 rpm. The time point at which SAL was added was set to 0 hours, and the state of the iron sulfide was observed. As a result, the iron sulfide was dissolved after 4 hours, and the reaction solution was colorless and transparent.

    <Example 2> Iron sulfide removal test (citral)    

The same test as in Example 1 was performed except that citral was used instead of SAL. After 7 hours, the iron sulfide was dissolved, and the reaction solution was colorless and transparent.

    <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, the iron sulfide was dissolved, and the reaction solution was colorless and transparent.

    <Test Example 1> Thermal stability test    

Put SAL and acrolein into 50mL three-necked flasks respectively, raise the temperature to 50 ° C under nitrogen environment, and use the calibration curve method obtained by internal standard gas chromatography to observe the SAL and acrolein content after heating up. Change in content at 100%. The results are shown in Table 1.

    [Gas chromatography analysis]    

Analysis equipment: GC-14A (manufactured by Shimadzu Corporation)

Detector: FID (hydrogen flame ionization detector)

Use column: DB-1701 (length: 50m, film thickness 1μm, inner diameter 0.32mm) (manufactured by Agilent Technologies)

Analysis conditions: Inject.Temp.250 ℃, Detect.Temp.250 ℃

Heating conditions: 70 ℃ → (heating at 5 ℃ / min) → 250 ℃

Internal standard substance: Diglyme (diethylene glycol dimethyl ether)

After 10 hours, acrolein was lost by 3.4% relative to the remaining 99.9% of SAL despite the hydroquinone as a stabilizer. From this result, it is understood that the thermal stability of SAL is much higher than that of acrolein.

    <Test Example 2> pH stability test    

SAL and acrolein were each dissolved in 0.5 mol / L phosphate buffer solution having different pHs to prepare a 0.1 wt% solution. Put 50 mL of this solution into a sample bottle under a nitrogen environment, store it at 23 ± 2 ° C, and use the absolute calibration curve obtained by high-speed liquid permeation chromatography analysis to observe the SAL and acrolein content at the time of preparation. Change in content at 100%. The results are shown in FIGS. 1 and 2.

From this result, it turns out that pH stability of SAL is much higher than acrolein.

    [Preparation of phosphate buffer]    

pH1.7: Make 4.9g of 75% phosphoric acid and 7.8g of sodium dihydrogen phosphate. The dihydrate was dissolved in 200 mL of distilled water.

pH6.2: Make 7.8g of sodium dihydrogen phosphate. Dihydrate, 7.1 g of disodium hydrogen phosphate were dissolved in 200 mL of distilled water.

pH8.1: Make 0.3g of sodium dihydrogen phosphate. Dihydrate and 13.9 g of disodium hydrogen phosphate were dissolved in 200 mL of distilled water.

    [High-speed liquid permeation chromatography analysis]    

Analysis equipment: Prominence system (manufactured by Shimadzu Corporation)

Use column: Cadenza CD-C18 (length: 150m, inner diameter 4.6mm)

Developing solution: H ₂ O / MeOH = 45 / 55vol ratio, H ₃ PO ₄ = 1mol / L

Flow rate: 1mL / min

    <Reference example>    

SAL, citral and acrolein are existing compounds, and information on safety has been revealed. Information on security is shown in Table 2 as a reference. Compared to acrolein, SAL or citral are known to be extremely low toxic and safe.

From the above examples, comparative examples, test examples, and reference examples, it can be seen that aldehydes (1) such as SAL have the same iron sulfide removal ability as acrolein, higher thermal stability and pH stability than acrolein, and are safe. .

Industrial availability

The composition of the present invention has high thermal stability and pH stability, and is useful in that iron sulfide can be safely and efficiently removed.

Claims (7)

A composition for removing iron sulfide, which contains an α, β-unsaturated aldehyde represented by the following general formula (1) as an active ingredient, (R ¹ to R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms; wherein R ¹ and R ² or R ³ They are connected to each other to form an alkylene group having 2 to 6 carbon atoms, and R ¹ and R ^{2 are} not hydrogen atoms at the same time). For example, the composition of claim 1, wherein R ¹ to R ³ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The composition of claim 1 or 2, wherein R ³ is a hydrogen atom.     A method for removing iron sulfide, characterized in that the composition according to any one of claims 1 to 3 is contacted with iron sulfide.         The method according to claim 4, wherein the α, β-unsaturated aldehyde in the composition is added to 1 to 100 parts by mass relative to 1 part by mass of iron sulfide.         The method according to claim 4 or 5, which involves contacting the α, β-unsaturated aldehyde in the composition with iron sulfide in a range of -30 ° C to 150 ° C.         A use according to any one of claims 1 to 3 for removing iron sulfide.