COMPOSITION FOR REMOVING IRON SULFIDE

Abstract

Provided is a composition for removing iron sulfide, containing, as an active ingredient, an ,-unsaturated aldehyde represented by the following general formula (1):

##STR00001##

wherein R.sup.1 to R.sup.3 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, provided that R.sup.1 may be connected to R.sup.2 or R.sup.3, to constitute an alkylene group having 2 to 6 carbon atoms; and that R.sup.1 and R.sup.2 are not a hydrogen atom at the same time.

Claims

1. A composition for removing iron sulfide, the composition comprising, as an active ingredient, an ,-unsaturated aldehyde represented by formula (1): ##STR00003## wherein R.sup.1 to R.sup.3 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, provided that R.sup.1 is optionally connected to R.sup.2 or R.sup.3 to constitute an alkylene group having 2 to 6 carbon atoms and that R.sup.1 and R.sup.2 are not a hydrogen atom at the same time.

2. The composition according to claim 1, wherein R.sup.1 to R.sup.3 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

3. The composition according to claim 1, wherein R.sup.3 is a hydrogen atom.

4. A method for removing iron sulfide, the method comprising contacting the composition of claim 1 with iron sulfide.

5. The method according to claim 4, wherein the ,-unsaturated aldehyde in the composition is added in an amount of 0.1 to 100 parts by mass based on 1 part by mass of iron sulfide.

6. The method according to claim 4, wherein said contacting occurs at a temperature of from 30 C. to 150 C.

7. A method for removing iron sulfide, the method comprising removing iron sulfide using the composition according to claim 1.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0010] FIG. 1 is a graph showing pH stability of senecioaldehyde (SAL).

[0011] FIG. 2 is a graph showing pH stability of acrolein.

DESCRIPTION OF EMBODIMENTS

[0012] The composition of the present invention includes the aldehyde (1) as an active ingredient.

[0013] In the aldehyde (1), the alkyl group having 1 to 10 carbon atoms, which R.sup.1 to R.sup.3 each independently represent, may be linear, branched, or cyclic, and examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a t-butyl group, a n-pentyl group, a n-hexyl group, a n-octyl group, a n-decyl group, a n-dodecyl group, and a cyclopentyl group. Above all, from the viewpoint of removal performance of iron sulfide, a methyl group, an ethyl group, or a n-propyl group is preferred, a methyl group or an ethyl group is more preferred, and a methyl group is still more preferred.

[0014] The alkenyl group having 2 to 10 carbon atoms, which R.sup.1 to R.sup.3 each independently represent, may be linear, branched, or cyclic, and examples thereof include a vinyl group, an allyl group, a 1-penten-1-yl group, a 4-methyl-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-decen-1-yl group. Above all, an alkenyl group having 1 to 8 carbon atoms is preferred, and an alkenyl group having 1 to 6 carbon atoms is more preferred.

[0015] Examples of the aryl group having 6 to 12 carbon atoms, which R.sup.1 to R.sup.3 each independently represent, include a phenyl group, a tolyl group, an ethylphenyl group, a xylyl group, a trimethylphenyl group, a naphthyl group, a biphenylyl group. Above all, an aryl group having 6 to 10 carbon atoms is preferred.

[0016] In the case where R.sup.1 is connected to R.sup.2 or R.sup.3, to constitute an alkylene group having 2 to 6 carbon atoms, examples of the alkylene group include an ethylene group, a n-propylene group, a n-butylene group, a n-pentylene group, a hexylene group, a 2-methylethylene group, a 1,2-dimethylethylene group, a 2-methyl-n-propylene group, a 2,2-dimethyl-n-propylene group, and a 3-methyl-n-pentylene group.

[0017] It is preferred that R.sup.1 to R.sup.3 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0018] From the viewpoint of exhibiting removal performance of iron sulfide and keeping thermal stability and pH stability, it is preferred that at least one of R.sup.1 and R.sup.2 is a methyl group, and it is still more preferred that both R.sup.1 and R.sup.2 are a methyl group.

[0019] From the viewpoint of promoting the reaction with hydrogen sulfide and efficiently removing iron sulfide, it is preferred that R.sup.3 is a hydrogen atom.

[0020] 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-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-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 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-cyclopropylpyridenepropanal, 2-cyclopentylidenepropanal, 2-cyclopentylidenehexanal, 2-(3-methylcyclopentylidene)propanal, 2-cyclohexylidienepropanal, 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-trimethylcyclopentene, 1-formylcyclohexene, 1-formyl-3-methylcyclohexene, 1-formyl-4-methylcyclohexene, 1-formyl-5-methylcyclohexene, 1-formyl-6-methylcyclohexene, 1-formyl-3,3-dimethylcyclohexene, 1-formyl-5,5-dimethylcyclohexene, 1-formyl-2-methylcyclohexene, 1-formyl-2,5,6,6-tetramethylcyclohexene, 1-formyl-2,4,6,6-tetramethylcyclohexene, 1-formylcycloheptene, 1-formyl-2-methylcycloheptene, 1-formyl-3-methylcycloheptene, 1-formylcyclooctene, 2,4-pentadienal, 2,4-hexadienal, 2,5-hexadienal, 5-methyl-2,4-hexadienal, 2,4-heptadienal, 2,4-octadienal, 2,7-octadienal, 3,7-dimethyl-2,6-octadienal (citral), 2,4,6-octatrienal, 7-methyl-2,4,6-octatrienal, 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-tolyppropenal, 3-(p-tolyl)propenal, and 3-napthylpropenal. Above all, 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, and 3-propyl-2-hexenal are preferred; 3-methyl-2-butenal, 3-methyl-2-pentenal, and 3-ethyl-2-pentenal are more preferred; and 3-methyl-2-butenal (senecioaldehyde, hereinafter referred to simply as SAL) is still more preferred.

[0021] With respect to compounds having a trans-isomer and a cis-isomer, either one of them may be used, or a mixture of the both isomers may also be used. In the case of using a mixture, those having an arbitrary mixing ratio can be used.

[0022] As for the aldehyde (1), a commercially available product may be used, or it may be synthesized through an oxidative dehydrogenation reaction of a corresponding ,-unsaturated alcohol (see, for example, JP 60-224652 A).

[0023] Though a content proportion of the aldehyde (1) that is an active ingredient in the composition of the present invention can be properly set according to the use embodiment, it is typically 1 to 99.9% by mass, and from viewpoint of cost-effectiveness, it is preferably 5 to 99.9% by mass, and more preferably 5 to 95% by mass.

[0024] The composition of the present invention may contain other iron sulfide remover, such as acrolein, tetrakis(hydroxymethyl)phosphine or a corresponding phosphonium salt, hydrochloric acid, and formic acid, as long as the effects of the present invention are not impaired.

[0025] The composition of the present invention may contain an appropriate solvent, such as cyclohexane, toluene, xylene, a heavy aromatic naphtha, and a petroleum distillate; and a monoalcohol or dialcohol having 1 to 10 carbon atoms, e.g., methanol, ethanol, and ethylene glycol.

[0026] The composition of the present invention may contain, in addition to the aldehyde (1), a component, such as 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, a dehydration regulator, a swelling prevention agent, a scale inhibitor, a biocide, a friction reducer, a defoaming agent, an agent for preventing a lost circulation of mud water, a lubricating agent, a clay dispersant, a weighting agent, and a gelling agent, as long as the effects of the present invention are not impaired.

[0027] The composition of the present invention is not particularly limited with respect to its production method, and it can be, for example, produced by adding and mixing the aldehyde (1) with the aforementioned arbitrary component, such as an iron sulfide remover and a solvent.

[0028] Though the composition of the present invention is suitably a liquid, it may be converted in a solid form, such as a powder and a fluid, upon being properly supported on a carrier, etc., according to a form to be used for the purpose of removing iron sulfide.

[0029] As a preferred embodiment of the present invention, the treatment is performed by adding the composition of the present invention in an amount sufficient for the removal of iron sulfide to a liquid containing iron sulfide. In the method of removing iron sulfide by using the composition of the present invention, the composition of the present invention is added such that the amount of the aldehyde (1) contained in the composition of the present invention is preferably 0.1 to 100 parts by mass, and more preferably 2 to 100 parts by mass based on 1 part by mass of iron sulfide. A temperature on the occasion of performing the treatment in which the composition of the present invention is added to and brought into contact with a liquid containing iron sulfide is preferably in a range of from 0 C. to 150 C., and more preferably from 20 C. to 130 C.

EXAMPLES

[0030] The present invention is hereunder specifically described by reference to Examples and the like, but it should be construed that the present invention is by no means limited by the following Examples. SAL, citral, and acrolein used in the Examples and Comparative Example are those mentioned below.

[0031] SAL: One synthesized from prenol in conformity with the method described in JP 60-224652 A (purity: 98.1%)

[0032] Citral: Product available from Kuraray Co., Ltd. (purity: 98.0%, trans/cis=51/49 to 57/43 (molar ratio))

[0033] Acrolein: Product available from Tokyo Chemical Industry Co., Ltd., which contains hydroquinone as a stabilizer

<Example 1> Removal Test of Iron Sulfide (SAL)

[0034] 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 nonahydrate, and 138.2 (0.5 mmol) of iron sulfate heptahydrate were added and stirred. As a result, iron sulfide was produced as a fine black precipitate. 126.3 mg (1.5 mmol) of SAL was added thereto, and the reaction solution was subjected to temperature rise to 50 C. while stirring at 500 rpm. The point of time at when SAL was added was defined as 0 hour, and the behavior of iron sulfide was observed. As a result, after elapsing 4 hours, the iron sulfide was dissolved, and the reaction solution became colorless transparent.

<Example 2> Removal Test of Iron Sulfide (Citral)

[0035] The same test as in Example 1 was carried out, except that citral was used in place of SAL. After elapsing 7 hours, iron sulfide was dissolved, and the reaction solution became colorless transparent.

<Comparative Example 1> Removal Test of Iron Sulfide (Acrolein)

[0036] The same test as in Example 1 was carried out, except that acrolein was used in place of SAL. After elapsing 4 hours, iron sulfide was dissolved, and the reaction solution became colorless transparent.

<Test Example 1> Thermal Stability Test

[0037] 50 mL of each of SAL and acrolein was charged in three-necked flask, and the contents were subjected to temperature rise to 50 C. in a nitrogen atmosphere. On the occasion when the content of each of SAL and acrolein immediately after the temperature rise was defined as 100%, a change of the content ratio was observed according to the calibration curve method by means of gas chromatography with an internal standard. The results are shown in Table 1.

[Gas Chromatography Analysis]

[0038] Analysis instrument: GC-14A (available from Shimadzu Corporation)
Detector: FID (hydrogen flame ionization detector)

[0039] Column used: DB-1701 (length: 50 m, film thickness: 1 pn, inner diameter: 0.32 mm) (available from Agilent Technologies)

[0040] Analysis conditions: Injection temperature: 250 C., detection temperature: 250 C.

[0041] Temperature rise conditions: 70 C..fwdarw.(temperature rise at 5 C./min).fwdarw.250 C.

[0042] Internal standard substance: Diglyme (diethylene glycol dimethyl ether)

TABLE-US-00001 TABLE 1 Results of thermal stability test 2 hours 4 hours 6 hours 10 hours 0 hour elapsed elapsed elapsed elapsed SAL 100.0% 100.0% 100.0% 100.0% 99.9% Acrolein 100.0% 99.5% 98.3% 98.1% 96.6%

[0043] After elapsing 10 hours, SAL remained in a ratio of 99.9%, whereas nevertheless acrolein contained hydroquinone as a stabilizer, it was lost in a ratio of 3.4%. It is noted from these results that SAL is extremely high in the thermal stability as compared with acrolein.

<Test Example 2> pH Stability Test

[0044] Each of SAL and acrolein was dissolved in 0.5 mol/L of phosphoric acid buffer solutions having a pH different from each other, thereby preparing 0.1 wt % solutions. 50 mL of each of the solutions was charged in a sample vial in a nitrogen atmosphere and stored at 232 C. On the occasion when the content of each of SAL and acrolein at the time of preparation was defined as 100%, a change of the content ratio was observed according to the absolute calibration curve by means of high-performance liquid chromatography analysis. The results are shown in FIGS. 1 and 2.

[0045] It is noted from these results that SAL is extremely high in the pH stability as compared with acrolein.

[Preparation of Phosphoric Acid Buffer Solution]

[0046] 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.

[0047] 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.

[0048] 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.

[High-Performance Liquid Chromatography Analysis]

[0049] Analysis instrument: Prominence System (available from Shimadzu Corporation)

[0050] Column used: Cadenza CD-C18 (length: 150 m, inner diameter: 4.6 mm)

[0051] Developing solution: H.sub.2O/MeOH=45/55 (volume ratio), H.sub.3PO.sub.4=1 mol/L

[0052] Flow rate: 1 mL/min

Reference Example

[0053] SAL, citral, and acrolein are each an existing compound, and the information regarding the safety is disclosed. For reference, the information regarding the safety is shown in Table 2. SAL and citral are extremely low in the toxicity and safe as compared with acrolein.

TABLE-US-00002 TABLE 2 Information regarding safety of SAL, citral, and acrolein SAL Citral Acrolein Fire Service Act Category IV, Class II petroleum Category IV, Class III petroleum Category IV, Class I petroleum Hazardous grade III, water-insoluble Hazardous grade III, water-insoluble Hazardous grade II, water-insoluble Poisonous and Deleterious Not applicable Not applicable Poisonous substance Substances Control Law United Nations Classification Class 3 (inflammable liquid) Not applicable Class 6.1 (poisonous substance) Acute toxicity Rat LD50: 690 mg/kg Rat LD50: 4,960 mg/kg Rat LD50: 42 mg/kg Permissible Exposure Limit GHS Classification; Section 1 (upper No information 0.1 ppm respiratory tract) Respiratory organs, nervous system, Irritative symptom in respiratory tract at and liver are considered to be target 100 ppm or more organs Anesthetic action

[0054] It is noted from the aforementioned Examples, Comparative Example, and Reference Example that the aldehyde (1), such as SAL, has an iron sulfide removal ability equivalent to acrolein and is higher in the thermal stability and the pH stability and safer than acrolein.

INDUSTRIAL APPLICABILITY

[0055] The composition of the present invention is useful in view of the fact that it is high in the thermal stability and the pH stability and is able to remove iron sulfide safely and efficiently.