Note: Descriptions are shown in the official language in which they were submitted.
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DESCRIPTION
Title of Invention
COMPOSITION FOR REMOVING IRON SULFIDE
Technical Field
[0001]
The present invention relates to a composition for removing iron sulfide
and a method for removing iron sulfide, which includes using the same.
Background Art
[0002]
Hydrogen sulfide that often exists in hydrocarbons, such as fossil fuels
and refined petroleum products, for example, 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
concentrates,
corrodes iron which is used in excavation facilities, etc., to cause
generation of
iron sulfide. The iron sulfide is accumulated as a deposit within production
facilities of fossil fuels and refined petroleum products, to lower
operational
efficiency of instruments in heat exchanger, cooling tower, reactor,
transmission pipeline, furnace, etc., or disturb precise measurement for
facility
maintenance, and therefore, it is desired to remove this.
[0003]
As a method for removing iron sulfide, a method of dissolving iron
sulfide with acrolein is known, and announcement regarding the removal of
iron sulfide with acrolein as an active ingredient is also made in SPE Annual
Technical Conference and Exhibition SPE 146080, held in the city of Denver,
Colorado, USA on October 30 to November 2, 2011 (NPL 1). However, the
acrolein is a compound which is strongly toxic and whose concentration is
strictly regulated from the viewpoint of occupational safety and from the
viewpoint of environmental safety, so that it involves such a problem that
attention is required for handling. In addition to the above, the acrolein is
problematic from the viewpoint that it is extremely easily polymerized and
lacks in thermal stability and also from the viewpoint that it lacks in pH
stability, so that its abundance gradually decreases depending upon the pH of
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=
the environment to be used.
Citation List
Non-Patent Literature
[0004]
NPL 1; SPE Annual Technical Conference and Exhibition SPE 146080,
2011; http://dx.doi.org/10.2118/146080-MS
Summary of Invention
Technical Problem
[0005]
In the light of the above, in using acrolein for the purpose of removing
iron sulfide, there are problems from the viewpoint of safety and thermal
stability and also from the viewpoint of pH stability, and therefore, a safer
and
more stable compound is desired as a substitute therefor. Now, an object of
the
present invention is to provide a composition containing an active ingredient
with high thermal stability and pH stability and being capable of removing
iron
sulfide safely and efficiently.
Solution to Problem
[0006]
In accordance with the present invention, the aforementioned object is
achieved by the following [1] to [7].
[1] A composition for removing iron sulfide, containing, as an active
ingredient,
an a,p-unsaturated aldehyde represented by the following general formula (1)
(hereinafter referred to as "aldehyde (1)");
[0007]
R2
(1)
R3
[0008]
wherein RI- to R3 each independently represent a hydrogen atom, an
alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10
carbon atoms, or an aryl group having 6 to 12 carbon atoms, provided that R1
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may be connected to R2 or R3, to constitute an alkylene group having 2 to 6
carbon atoms; and that R1 and R2 are not a hydrogen atom at the same time.
[2] The composition of [1], wherein R1 to R3 are each independently a hydrogen
atom or an alkyl group having 1 to 5 carbon atoms.
[3] The composition of [1] or [2], wherein R3 is a hydrogen atom.
[4] A method for removing iron sulfide, including bringing the composition of
any of [1] to [3] into contact with iron sulfide.
[5] The method of [4], wherein the aldehyde (1) in the composition is added in
an amount of 0.1 to 100 parts by mass based on 1 part by mass of iron sulfide.
[6] The method of [4] or [5], including bringing the aldehyde (1) in the
composition into contact with iron sulfide in a range of from -30 C to 150 C.
[7] Use of the composition of any of [1] to [3], for removing iron sulfide.
Advantageous Effects of Invention
[0009]
Since the composition of the present invention contains the aldehyde (1),
an excellent removal performance of iron sulfide is exhibited.
In particular, as compared with a conventional iron sulfide remover
containing acrolein, the composition of the present invention has such an
advantage that it is extremely low in toxicity and high in thermal stability
and
pH stability. Though the reasons for this are not elucidated yet, it may be
considered as one of factors that since the aldehyde (1) has at least one of
an
alkyl group, an alkenyl group, and an aryl group at the f3-position thereof,
an
addition reaction to the 3-position of a bulky molecule, such as a biomolecule
and a propagating chain, is hard to occur as compared with acrolein not having
a substituent at the V-position thereof. Meanwhile, with respect to the
removal
of iron sulfide, it may be considered that the aldehyde (1) comes to bond to
hydrogen sulfide that is existent in an equilibrium state with iron sulfide to
thereby remove hydrogen sulfide, dissolution of iron sulfide is promoted, and
as
a result, the iron sulfide is removed; and while the aldehyde (1) has a
substituent at the 13-position thereof, an attack from hydrogen sulfide that
is in
general a small molecule is not hindered so much, whereby the removal
performance of iron sulfide is kept.
Brief Description of Drawings
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, =
[0010]
r
' Fig. 1 is a graph showing pH stability of senecioaldehyde
(SAL).
Fig. 2 is a graph showing pH stability of acrolein.
Description of Embodiments
[0011]
The composition of the present invention includes the aldehyde (1) as
an active ingredient.
In the aldehyde (1), the alkyl group having 1 to 10 carbon atoms, which
Ri- to R3 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.
The alkenyl group having 2 to 10 carbon atoms, which R1 to R3 each
independently represent, may be linear, branched, or cyclic, and examples
thereof include a vinyl group, an allyl group, a 1-penten-1-y1 group, a
4-methyl-3-penten-1-y1 group, a 4-penten-1-y1 group, a 1-hexen-1-y1 group, a
1-octen-1-y1 group, and a 1-decen-1-y1 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.
Examples of the aryl group having 6 to 12 carbon atoms, which 11,1- to R3
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.
In the case where R1 is connected to R2 or R3, 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.
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It is preferred that RI- to R3 are each independently a hydrogen atom or
, an alkyl group having 1 to 5 carbon atoms.
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 RI- and R2 is a methyl group, and it is still more preferred that both RI-
and R2
are a methyl group.
From the viewpoint of promoting the reaction with hydrogen sulfide and
efficiently removing iron sulfide, it is preferred that R3 is a hydrogen atom.
[0012]
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-dimethy1-2-pentenal, 6-mehy1-2-heptenal,
4-ethyl-2-hexenal,
2-methyl-2-butenal, 2-methyl-2-
pentenal, 2-methyl-2-hexenal,
2-methyl-2-heptenal, 2-methy1-2-octenal,
4-methyl-2-propy1-2-hexenal,
2,4-dimethy1-2-pentenal, 2,4-dimethy1-2-hexenal, 2,4-dimethy1-2-heptenal,
2,5-dimethy1-2-hexenal, 2,6-dimethy1-2-heptenal, 2,4,4-trimethy1-2-pentena1,
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-methy1-2-hexenal,
2-propy1-2-butenal, 2-propy1-2-
pentenal, 2-propy1-2-hexenal,
2-propy1-2-heptenal,
2-propy1-4-methyl-2-pentenal,
2-propy1-5-methy1-2-hexenal,
2-isopropyl-2-butenal,
2-isopropyl- 4-methyl- 2-pe ntenal,
2-isopropyl-4-methyl-2-hexenal,
2-isopropyl- 5- methy1-2-hexenal, 2-butyl-2-
butenal, 2 -buty1-2-pentenal,
2-butyl-2-hexenal, 2-butyl-2-heptenal, 2-butyl-2-octenal, 2-isobuty1-2-
heptenal,
2-isobuty1-6-methyl-2-heptenal, 2-penty1-2-
butenal, 2-penty1-2-pentenal,
2-penty1-2-hexenal, 2-penty1-2-
heptenal, 2-penty1-2-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-methy1-2-dodecena1,
3-methy1-2-tridecena1, 3-ethyl-2-pentenal,
3,4-dimethy1-2-pentenal,
3,4,4-trimethy1-2-pentenal,
3-isopropy1-4-methy1-2-pentena1,
3-ethyl-2-hexenal, 3-propy1-2-hexenal,
3,5-dimethy1-2-hexenal,
3-(t-butyl) -4,4-dimethy1-2-pentenal,
3-butyl-2-heptenal,
2,3-dimethy1-2-butenal,
2-ethy1-3-methy1-2-butena1,
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=
2-isopropyl- 3-methy1-2-butena1, 2,
3- dimethy1-2-pentenal,
2,3, 4-trimethy1-2 -hexenal, 2-
isobutyl- 3-methyl- 2-butenal,
3-methyl- 2-p entyl- 2-pentenal, 2,3-
diethyl- 2-heptenal,
2-(1,1-dimethylpropy1)-3-methy1-2-butenal, 3,
5,5-trimethyl- 2-hexenal,
2,3,4-trimethy1-2-pentena1, 2-
cyclopropylpyridenepropanal,
2-cyclopentylidenepropanal, 2-
cyclopentylidenehexanal,
2- (3- methylcyclopentylidene)prop anal, 2-
cyclohexylidienepropanal,
2-(2-methylcyclohexylidene)propanal, 2-
cyclohexylidenebutanal,
2-cyclohexylidenehexanal, 1-
formylcyclobutene,
1- formyl- 3,3 - dimethylcyclobutene, 1-
cyclopropy1-2-formylcyclobutene,
1- formylcyclop entene, 5-
ethyl- 1-formylcyclopentene,
1- formyl- 3- methylcyclopentene, 1-
formy1-4-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-
formy1-2, 5,6, 6-tetramethylcyclohexene,
1-formy1-2,4,6,6-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- dimethy1-2,7-nonadienal, 2,4-decadienal, 2,4-
undecadienal,
2,4-dodecadienal, 2,4-tridecadienal, 2,4,7-tridecatrienal, 3-phenylpropenal,
3-phenyl-2-methylpropenal, 3-(o-tolyl)propenal, 3-(p-tolyl)propenal, and
3-napthylpropenal. Above all, 3-methyl-2-butenal, 3-methyl-2-pentenal,
3 -methyl- 2 - hexenal, 3-methy1-2-heptena1, 3-
methyl-2-octenal,
3,7-dimethy1-2,6-octadienal (citral), 3-ethyl-2-pentenal, 3-ethyl-2-hexenal,
and
3-propy1-2-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
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preferred.
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.
[0013]
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 a,13-unsaturated alcohol (see, for example, JP 60-224652 A).
[0014]
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.
[0015]
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.
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.
[0016]
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.
[0017]
The composition of the present invention is not particularly limited
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. .
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.
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.
[0018]
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
[0019]
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.
SAL: One synthesized from prenol in conformity with the method
described in JP 60-224652 A (purity: 98.1%)
Citral: Product available from Kuraray Co., Ltd. (purity: 98.0%,
trans/cis = 51/49 to 57/43 (molar ratio))
Acrolein: Product available from Tokyo Chemical Industry Co., Ltd.,
which contains hydroquinone as a stabilizer
[0020]
<Example 1> Removal Test of Iron Sulfide (SAL)
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In a 1L 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.
[0021]
<Example 2> Removal Test of Iron Sulfide (Citral)
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.
[0022]
<Comparative Example 1> Removal Test of Iron Sulfide (Acrolein)
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.
[0023]
<Test Example 1> Thermal Stability Test
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.
[0024]
[Gas Chromatography Analysis]
Analysis instrument: GC-14A (available from Shimadzu Corporation)
Detector: FID (hydrogen flame ionization detector)
Column used: DB-1701 (length: 50 m, film thickness: 1 1.im, inner
diameter: 0.32 mm) (available from Agilent Technologies)
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Analysis conditions: Injection temperature: 250 C, detection
temperature: 250 C
Temperature rise conditions: 70 C ¨> (temperature rise at 5 C/min) ¨>
250 C
Internal standard substance: Diglyme (diethylene glycol dimethyl
ether)
[0025]
Table 1: Results of thermal stability test
0 h 2 hours 4 hours 6 hours 10
hours
our
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%
[0026]
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.
[0027]
<Test Example 2> pH Stability Test
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 23 2 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.
It is noted from these results that SAL is extremely high in the pH
stability as compared with acrolein.
[0028]
[Preparation of Phosphoric Acid Buffer Solution]
pH 1.7: 4.9 g of 75% phosphoric acid and 7.8 g of sodium dihydrogen
phosphate dihydrate were dissolved in 200 mL of distilled water.
pH 6.2: 7.8 g of sodium dihydrogen phosphate dihydrate and 7.1 g of
disodium hydrogen phosphate were dissolved in 200 mL of distilled water.
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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.
[0029]
[High-Performance Liquid Chromatography Analysis]
Analysis instrument: Prominence System (available from Shimadzu
Corporation)
Column used: Cadenza CD-C18 (length: 150 m, inner diameter: 4.6 mm)
Developing solution: H20/Me0H = 45/55 (volume ratio), H3PO4 = 1
mol/L
Flow rate: 1 mL/min
[0030]
<Reference Example>
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.
12
[00311
Table 2: Information regarding safety of SAL, citral, and acrolein
SAL Citral
Acrolein
Category IV, Class II petroleum Category IV,
Class III petroleum Category IV, Class I petroleum
Fire Service Act
Hazardous grade III, water-insoluble Hazardous grade
III, water-insoluble Hazardous grade II, water-insoluble
Poisonous and Deleterious Substances
Control Law Not applicable Not
applicable Poisonous substance
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
GHS Classification; Section 1 (upper
0.1 ppm
Respiratory organs, nervous system,
Permissible Exposure Limit respiratory tract) No
information and liver are considered to be target
Irritative symptom in respiratory tract at
organs
100 ppm or more
Anesthetic action
.
,õ
,õ
,õ
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[00321
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
[0033]
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.
