WO2019208311A1 - Composition for eliminating sulfur-containing compound - Google Patents

Abstract

A composition for eliminating a sulfur-containing compound included in at least one among a liquid and a gas, wherein the sulfur-containing compound is at least one selected from the group consisting of hydrogen sulfide and compounds containing an -SH group, and the composition is at least one among a saturated aldehyde and a specific acid.

Description

Composition for removing sulfur-containing compounds

The present invention relates to a composition for removing a sulfur-containing compound contained in at least one of a liquid and a gas.

Natural gas, liquefied natural gas, sour gas, crude oil, naphtha, heavy aromatic naphtha, gasoline, kerosene, diesel oil, light oil, heavy oil, FCC slurry, asphalt, hydrocarbons such as refined petroleum products such as oilfield concentrate Often contain sulfur-containing compounds such as various compounds containing hydrogen sulfide and —SH groups (typically various mercaptans).

Above all, the toxicity of hydrogen sulfide is well known, and in the industry dealing with fossil fuels and refined petroleum products, considerable costs and efforts are made to reduce the hydrogen sulfide content to a safe level. For example, for pipeline gas, it is required as a general regulation value that the content of hydrogen sulfide does not exceed 4 mass ppm.

Also, various compounds containing hydrogen sulfide and —SH groups tend to leak into the atmosphere due to their volatility. Therefore, the bad odor of the compound has become a problem in hydrocarbon storage locations, the surroundings, pipelines, and shipping systems. In addition, various compounds containing hydrogen sulfide and —SH groups are also present in water such as sewage, and malodor derived therefrom is often a problem.

For the problem derived from such a sulfur-containing compound, for example, a method for removing hydrogen sulfide in hydrocarbons using triazine has been proposed for a long time. However, although a basic sulfur-containing compound remover such as triazine exhibits good removal efficiency, it has a problem of promoting precipitation of insoluble calcium carbonate in an environment where carbon dioxide is present.

Precipitation of calcium carbonate is a problem as a cause of clogging of piping and a decrease in productivity, particularly in the field of crude oil drilling and the like.

However, calcium carbonate has a very low solubility product of 3.6 × 10 ⁻⁹ mol ² dm ^−6, and easily precipitates in an environment where calcium ions and carbonate ions (CO ₃ ²⁻ ) are present. Happens. In particular, calcium ions are generally contained in groundwater and seawater, and carbonate ions are easily generated in an environment in which carbon dioxide dissolves in water, so that it is not easy to suppress the precipitation of calcium carbonate.

In particular, when the aqueous solution becomes basic, carbonate ions are easily generated and calcium carbonate is likely to be precipitated. Usually, carbon dioxide in an aqueous solution exists in the form of carbonic acid (H ₂ CO ₃ ), hydrogen carbonate ion (HCO ₃ ⁻ ), and carbonate ion (CO ₃ ²⁻ ), and its distribution ratio depends on the pH of the aqueous solution. . That is, carbonate ions are scarcely present in the aqueous solution in the acidic region of pH <7, but in the basic region of pH> 7, the distribution ratio increases as the pH increases.

Therefore, when triazine, which is a basic sulfur-containing compound remover as described above, is used, the inside of the system becomes basic, and an environment in which calcium carbonate is likely to precipitate is obtained. Therefore, the problem of clogging of piping and a decrease in productivity becomes significant (Non-Patent Document 1).

On the other hand, as another method for removing hydrogen sulfide in hydrocarbons, a method using an aldehyde compound has been proposed for a long time. Specifically, Patent Document 1 discloses a reaction between an aldehyde compound and hydrogen sulfide, particularly a reaction between an aqueous formaldehyde solution and hydrogen sulfide, in an aqueous solution having a pH in the range of 2 to 12.

In the case of such a method, the problem of precipitation of calcium carbonate as described above is relatively less likely to occur, but the removal efficiency of sulfur-containing compounds such as hydrogen sulfide is not sufficient, and the precipitation of calcium carbonate is suppressed while suppressing precipitation. A technique that can improve the removal efficiency of sulfur compounds is desired.

US Pat. No. 1,991,765

PRODUCTION CHEMICALS FOR THE OIL AND GAS INDUSTRY 2nd ed. , Pp. 52-53

Therefore, an object of the present invention is to provide a composition that is excellent in the removal efficiency of sulfur-containing compounds contained in at least one of liquid and gas and that can suppress the precipitation of calcium carbonate.

As a result of intensive studies, the present inventors have found that by using a saturated aldehyde and a specific acid in combination, the removal efficiency of sulfur-containing compounds contained in at least one of a liquid and a gas, compared to the case where a saturated aldehyde is used alone. It was found that the precipitation of calcium carbonate can be further suppressed and the present invention has been completed.

（上記式（１）中、Ｒ^１及びＲ^２はそれぞれ独立して水素原子又は炭素数１～２４の炭化水素基を表す。上記式（２）中、Ｒ^３は水素原子又はリン酸基を表し、Ｒ^４は水素原子又は炭素数１～２４の炭化水素基を表す。上記式（３）中、Ｒ^５は水酸基又は炭素数１～２４の炭化水素基を表す。）
　［２］　前記炭化水素基は、アルキル基、アルケニル基又はアリール基である、上記［１］に記載の組成物。
　［３］　前記飽和アルデヒドと前記酸との含有量の比は、前記飽和アルデヒドをＡ（質量部）、前記酸をＢ（質量部）とした場合、Ａ：Ｂ＝０．１：９９．９～９９．９：０．１である、上記［１］又は［２］に記載の組成物。
　［４］　前記飽和アルデヒドが、アセトアルデヒド、プロピオンアルデヒド、ブタナール、イソブチルアルデヒド、ペンタナール、２－メチルブタナール、３－メチルブタナール、ヘキサナール、ヘプタナール、オクタナール、マロンジアルデヒド、スクシンアルデヒド、３－メチルグルタルアルデヒド、１，６－ヘキサンジアール、１，９－ノナンジアール及び２－メチル－１，８－オクタンジアールからなる群から選択される少なくとも１つである、上記［１］～［３］のいずれか１項に記載の組成物。
　［５］　前記飽和アルデヒドが、炭素数６以上の飽和アルデヒドである、上記［１］～［４］のいずれか１項に記載の組成物。
　［６］　前記液体及び気体のそれぞれが、炭化水素である、上記［１］～［５］のいずれか１項に記載の組成物。
　［７］　前記液体及び気体のそれぞれが、天然ガス、液化天然ガス（ＬＮＧ）、液化石油ガス（ＬＰＧ）、サワーガス、乾性ガス、湿性ガス、油田ガス、随伴ガス、テールガス、ジメチルエーテル、原油、ナフサ、重質芳香族ナフサ、ガソリン、ケロシン、ディーゼル油、軽油、潤滑油、重油、Ａ重油、Ｂ重油、Ｃ重油、ジェット燃料油、ＦＣＣスラリー、アスファルト、コンデンセート、ビチューメン、超重質油、タール、ガス液化油（ＧＴＬ）、石炭液化油（ＣＴＬ）、アスファルテン、芳香族炭化水素、アルキレート、基油、ケロジェン、コークス、黒油、合成原油、改質ガソリン、異性化ガソリン、再生重油、残油、白油、ラフィネート、ワックス、バイオマス燃料、バイオマス液化油（ＢＴＬ）、バイオガソリン、バイオエタノール、バイオＥＴＢＥ及びバイオディーゼルからなる群から選択される少なくとも１つである、上記［１］～［５］のいずれか１項に記載の組成物。
　［８］　液体及び気体の少なくとも一方に含まれる含硫黄化合物を除去する方法であって、
　前記含硫黄化合物が、硫化水素及び－ＳＨ基を含有する化合物からなる群から選択される少なくとも１つであり、
　上記［１］～［７］のいずれか１項に記載の組成物と、前記液体及び気体の少なくとも一方と、を接触させる、方法。
　［９］　前記組成物と、前記含硫黄化合物とを、－３０℃～１５０℃の範囲で接触させる、上記［８］に記載の方法。
　［１０］　液体及び気体の少なくとも一方に含まれる含硫黄化合物を除去するための、上記［１］～［７］のいずれか１項に記載の組成物の使用であって、
　前記含硫黄化合物が、硫化水素及び－ＳＨ基を含有する化合物からなる群から選択される少なくとも１つである、使用。 That is, the gist configuration of the present invention is as follows.
[1] A composition for removing a sulfur-containing compound contained in at least one of a liquid and a gas,
The sulfur-containing compound is at least one selected from the group consisting of hydrogen sulfide and a compound containing an —SH group;
The composition comprises a saturated aldehyde and at least one acid represented by any one of the following general formulas (1) to (3).

(In the above formula (1), R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms. In the above formula (2), R ³ represents a hydrogen atom or a phosphate group. R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms, and in the above formula (3), R ⁵ represents a hydroxyl group or a hydrocarbon group having 1 to 24 carbon atoms.
[2] The composition according to [1], wherein the hydrocarbon group is an alkyl group, an alkenyl group, or an aryl group.
[3] The content ratio between the saturated aldehyde and the acid is A: B = 0.1: 99.9 when the saturated aldehyde is A (parts by mass) and the acid is B (parts by mass). The composition according to the above [1] or [2], which is ˜99.9: 0.1.
[4] The saturated aldehyde is acetaldehyde, propionaldehyde, butanal, isobutyraldehyde, pentanal, 2-methylbutanal, 3-methylbutanal, hexanal, heptanal, octanal, malondialdehyde, succinaldehyde, 3-methylglutar Any one of [1] to [3] above, which is at least one selected from the group consisting of aldehyde, 1,6-hexane dial, 1,9-nonane dial, and 2-methyl-1,8-octane dial. The composition according to claim 1.
[5] The composition according to any one of [1] to [4], wherein the saturated aldehyde is a saturated aldehyde having 6 or more carbon atoms.
[6] The composition according to any one of [1] to [5] above, wherein each of the liquid and the gas is a hydrocarbon.
[7] Each of the liquid and gas is natural gas, liquefied natural gas (LNG), liquefied petroleum gas (LPG), sour gas, dry gas, wet gas, oil field gas, associated gas, tail gas, dimethyl ether, crude oil, naphtha, Heavy aromatic naphtha, gasoline, kerosene, diesel oil, light oil, lubricating oil, heavy oil, heavy fuel oil A, heavy fuel oil C, heavy fuel oil, jet fuel oil, FCC slurry, asphalt, condensate, bitumen, super heavy oil, tar, gas liquefaction Oil (GTL), coal liquefied oil (CTL), asphaltenes, aromatic hydrocarbons, alkylates, base oils, kerogen, coke, black oil, synthetic crude oil, reformed gasoline, isomerized gasoline, recycled heavy oil, residual oil, white Oil, raffinate, wax, biomass fuel, biomass liquefied oil (BTL), biogasoline, bioethanol The composition according to any one of [1] to [5] above, which is at least one selected from the group consisting of bio-ETBE and biodiesel.
[8] A method for removing a sulfur-containing compound contained in at least one of a liquid and a gas,
The sulfur-containing compound is at least one selected from the group consisting of hydrogen sulfide and a compound containing an —SH group;
A method of bringing the composition according to any one of [1] to [7] above into contact with at least one of the liquid and the gas.
[9] The method according to [8] above, wherein the composition and the sulfur-containing compound are contacted in the range of −30 ° C. to 150 ° C.
[10] Use of the composition according to any one of [1] to [7] above for removing a sulfur-containing compound contained in at least one of a liquid and a gas,
Use, wherein the sulfur-containing compound is at least one selected from the group consisting of a compound containing hydrogen sulfide and a —SH group.

According to the present invention, it is possible to provide a composition that is excellent in the removal efficiency of sulfur-containing compounds contained in at least one of liquid and gas and that can further suppress the precipitation of calcium carbonate.

（上記式（１）中、Ｒ^１及びＲ^２はそれぞれ独立して水素原子又は炭素数１～２４の炭化水素基を表す。上記式（２）中、Ｒ^３は水素原子又はリン酸基を表し、Ｒ^４は水素原子又は炭素数１～２４の炭化水素基を表す。上記式（３）中、Ｒ^５は水酸基又は炭素数１～２４の炭化水素基を表す。） The composition of the present invention is a composition for removing a sulfur-containing compound contained in at least one of a liquid and a gas, and is represented by a saturated aldehyde and any one of the following general formulas (1) to (3). At least one of the acids (hereinafter abbreviated as “specific acid”).

(In the above formula (1), R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms. In the above formula (2), R ³ represents a hydrogen atom or a phosphate group. R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms, and in the above formula (3), R ⁵ represents a hydroxyl group or a hydrocarbon group having 1 to 24 carbon atoms.

Here, the “sulfur-containing compound” is at least one selected from the group consisting of a compound containing hydrogen sulfide and an —SH group. The same applies to the following unless otherwise specified.

Since the composition of the present invention contains a saturated aldehyde and a specific acid as active ingredients, the removal efficiency of sulfur-containing compounds contained in at least one of liquid and gas (hereinafter simply referred to as “removal rate”) In addition, even when used in an environment where carbonate ions (CO ₃ ²⁻ ) are present, precipitation of calcium carbonate is suppressed.

In the present invention, the “composition” refers to a state in which a saturated aldehyde and a specific acid coexist in the same system. Here, “the state coexisting in the same system” refers to a state in which a saturated aldehyde and a specific acid are mixed in the same system, and is a target for using at least the composition of the present invention. It is sufficient that the saturated aldehyde and the specific acid are mixed at the time of contact with at least one of the liquid containing the sulfur-containing compound and the gas. That is, before contact with the liquid or the like, the saturated aldehyde and the specific acid may exist as separate components, for example, the saturated aldehyde and the specific acid with respect to the liquid. May be added individually and mixed in the liquid to constitute a composition. Moreover, you may comprise a composition by mixing a saturated aldehyde and a specific acid beforehand before making it contact with this liquid.

The reason why the composition of the present invention is superior in the removal efficiency of sulfur-containing compounds compared to conventional sulfur-containing compound removing agents containing aldehydes is not necessarily clear, but the addition reaction of sulfur-containing compounds to formyl groups is One of the factors is considered to be catalytically promoted by certain acids. Moreover, according to the composition of the present invention, the inside of the system can be kept acidic, so that the generation of calcium carbonate is also suppressed.

The composition of the present invention is for removing sulfur-containing compounds contained in at least one of liquid and gas.
In the present invention, the content of the sulfur-containing compound in the liquid or gas may be reduced from the initial amount by converting a sulfur-containing compound contained in at least one of the liquid and gas into another compound. To be removed. The converted product after being converted into another compound may remain in the system or may be separated out of the system.
As a typical removal method, for example, as described later, the composition of the present invention is brought into contact with at least one of a liquid and a gas containing a sulfur-containing compound, and then the composition after contact and the contact As a result, a method of reducing the content of the sulfur-containing compound in the liquid or gas from the initial amount can be mentioned.

Each of the liquid and gas to be used with the composition of the present invention is not particularly limited, and examples thereof include water and hydrocarbons, and hydrocarbons are preferable. Specific examples of liquid and gas include, for example, natural gas, liquefied natural gas (LNG), liquefied petroleum gas (LPG), sour gas, dry gas, wet gas, oil field gas, associated gas, tail gas, dimethyl ether, and crude oil. , Naphtha, heavy aromatic naphtha, gasoline, kerosene, diesel oil, diesel oil, lubricating oil, heavy oil, A heavy oil, B heavy oil, C heavy oil, jet fuel oil, FCC slurry, asphalt, condensate, bitumen, super heavy oil, tar Gas liquefied oil (GTL), coal liquefied oil (CTL), asphaltene, aromatic hydrocarbon, alkylate, base oil, kerogen, coke, black oil, synthetic crude oil, reformed gasoline, isomerized gasoline, recycled heavy oil, residual Oil, white oil, raffinate, wax, biomass fuel, biomass liquefied oil (BTL), biogasoline, Io ethanol, bio-ETBE, biodiesel, and the like. Each of the liquid and the gas may be only one type or two or more types.

In the present invention, the sulfur-containing compound to be removed is at least one selected from the group consisting of hydrogen sulfide and a compound containing an —SH group. That is, the target to be removed may be only hydrogen sulfide, only a compound containing an —SH group, or a mixture thereof. Here, the compound containing an —SH group is not particularly limited. For example, a sulfur-containing compound represented by the chemical formula “R—SH” (where R represents an organic group) and classified as a mercaptan Is mentioned. Examples of mercaptans represented by the chemical formula “R-SH” include methyl mercaptan, ethyl mercaptan, n-propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, isobutyl mercaptan, sec-butyl mercaptan, tert-butyl mercaptan, n- Examples thereof include those in which R is an alkyl group such as amyl mercaptan; those in which R is an aryl group such as phenyl mercaptan; and those in which R is an aralkyl group such as benzyl mercaptan. The compound containing the —SH group to be removed may be only one kind or two or more kinds.

The saturated aldehyde used in the present invention is not particularly limited. For example, formaldehyde, acetaldehyde, propionaldehyde, butanal, isobutyraldehyde, pentanal, 2-methylbutanal, 3-methylbutanal, hexanal, heptanal, octanal, nonanal, decanal, Monoaldehydes such as benzaldehyde; glyoxal, malondialdehyde, succinaldehyde, glutaraldehyde, 3-methylglutaraldehyde, 1,6-hexanedial, ethylpentanedial, 1,7-heptanedial, methylhexanedial 1,8-octane dial, methyl heptane dial, dimethyl hexane dial, ethyl hexane dial, 1,9-nonane dial, 2-methyl-1,8- Kutandial, ethyl heptane dial, 1,10-decandial, dimethyloctane dial, ethyloctane dial, dodecandial, hexadecandial, 1,2-cyclohexanedicarbaldehyde, 1,3-cyclohexanedicarbaldehyde, 1 , 4-cyclohexanedicarbaldehyde, 1,2-cyclooctanedicarbaldehyde, 1,3-cyclooctanedicarbaldehyde, 1,4-cyclooctanedicarbaldehyde, 1,5-cyclooctanedicarbaldehyde, etc. Examples include aldehydes. The saturated aldehyde may be used alone or in combination of two or more.

In particular, from the viewpoint of increasing the removal efficiency of sulfur-containing compounds, the saturated aldehyde used in the present invention is acetaldehyde, propionaldehyde, butanal, isobutyraldehyde, pentanal, 2-methylbutanal, 3-methylbutanal, hexanal, heptanal, octanal. , Nonanal, decanal, benzaldehyde, malondialdehyde, succinaldehyde, 3-methylglutaraldehyde, 1,6-hexanedial, ethylpentanedial, 1,7-heptanedial, methylhexanedial, 1,8 -Octane dial, methyl heptane dial, dimethyl hexane dial, ethyl hexane dial, 1,9-nonane dial, 2-methyl-1,8-octane dial, ethyl heptane dial, 1,1 -Preferably at least one compound selected from the group consisting of decandial, dimethyloctanedial, ethyloctanedial, dodecandial, 1,2-cyclohexanedicarbaldehyde and 1,4-cyclohexanedicarbaldehyde , Acetaldehyde, propionaldehyde, butanal, isobutyraldehyde, pentanal, 2-methylbutanal, 3-methylbutanal, hexanal, heptanal, octanal, malondialdehyde, succinaldehyde, 3-methylglutaraldehyde, 1,6-hexane More preferably, it is at least one compound selected from the group consisting of dial, 1,9-nonane dial and 2-methyl-1,8-octane dial. More specifically, there can be mentioned at least one compound selected from the group consisting of butanal, 1,9-nonane dial and 2-methyl-1,8-octane dial.

Further, from the viewpoint of high hydrophobicity and easy application to hydrocarbons, the saturated aldehyde used in the present invention is preferably a saturated aldehyde having 6 or more carbon atoms.

Furthermore, from the above two viewpoints, the saturated aldehyde used in the present invention is more preferably a saturated aldehyde having 6 to 12 carbon atoms, further preferably a saturated aldehyde having 6 to 10 carbon atoms, specifically, hexanal, heptanal. And at least one compound selected from the group consisting of octanal, 3-methylglutaraldehyde, 1,6-hexanediar, 1,9-nonanedial and 2-methyl-1,8-octanedial .

Among the above, from the viewpoints of low toxicity, biodegradability, handling safety, heat resistance, low metal corrosivity, etc., the saturated aldehydes include 1,9-nonanedial and 2-methyl-1,8- Particularly preferred is at least one compound selected from the group consisting of octane dials.

When at least one of 1,9-nonane dial and 2-methyl-1,8-octane dial is used as the saturated aldehyde, 1,9-nonane dial or 2-methyl-1,8-octane dial is used alone. Although it may be used, it is preferable to use 1,9-nonane dial and 2-methyl-1,8-octane dial as a mixture from the viewpoint of industrial availability. The mixing ratio of such a mixture of 1,9-nonanedial and 2-methyl-1,8-octanedial is not particularly limited, but is usually 1,9-nonanedial / 2-methyl-1,8-octanediar. The mass ratio is preferably 99/1 to 1/99, more preferably 95/5 to 5/95, still more preferably 93/10 to 45/55, and 90/10 to 55 / Particularly preferred is 45.

The sulfur-containing compound is removed from the liquid or gas by reacting the saturated aldehyde with the sulfur-containing compound. Although there is no restriction | limiting in particular in the form of the said reaction, For example, a sulfur-containing compound can carry out an addition reaction with respect to a formyl group.

　上記式（１）中、Ｒ^１及びＲ^２はそれぞれ独立して水素原子又は炭素数１～２４の炭化水素基を表す。上記式（２）中、Ｒ^３は水素原子又はリン酸基を表し、Ｒ^４は水素原子又は炭素数１～２４の炭化水素基を表す。上記式（３）中、Ｒ^５は水酸基又は炭素数１～２４の炭化水素基を表す。ここで、炭化水素基は、アルキル基、アルケニル基又はアリール基であることが好ましい。なお、炭化水素基は、無置換のものに限られず、置換基を有するものであってもよい。 The acid used in the present invention is represented by any one of the following general formulas (1) to (3).

In the above formula (1), R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms. In the above formula (2), R ³ represents a hydrogen atom or a phosphoric acid group, and R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms. In the above formula (3), R ⁵ represents a hydroxyl group or a hydrocarbon group having 1 to 24 carbon atoms. Here, the hydrocarbon group is preferably an alkyl group, an alkenyl group or an aryl group. The hydrocarbon group is not limited to an unsubstituted one, and may have a substituent.

The composition of the present invention contains the specific acid as described above, so that the inside of the system when reacting with the sulfur-containing compound can be kept acidic, and the precipitation of calcium carbonate can be effectively suppressed. it can. In addition, the specific acid as described above has a boiling point higher than that of an organic acid such as acetic acid. Therefore, the acid tends to accumulate in the kettle during the petroleum refining process, and the acid is mixed into the refined petroleum product. There is little fear.

In the compound represented by the general formula (1), R ¹ and R ² are each independently preferably a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and a hydrogen atom or a hydrocarbon having 1 to 12 carbon atoms. Groups are more preferred. Further, it is preferable that at least one of R ¹ and R ² are hydrogen atoms, and more preferably both are hydrogen atoms.
Examples of the compound represented by the general formula (1) include phosphoric acid, phosphoric acid (2-ethylhexyl), dodecyl phosphate, oleyl phosphate, ethyl phosphate, diphenyl phosphate, and the like. Particularly preferred.
In addition, when the compound represented by the said General formula (1) is an ester compound, it is preferable that a monoester is included at least, and it is more preferable that it consists only of a monoester.

In the compound represented by the general formula (2), R ³ represents a hydrogen atom or a phosphate group (such as —OPO ₃ H ₂ ), and a phosphate group is preferable. R ⁴ is preferably a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. Moreover, it is preferable that at least one of R ³ and R ⁴ is a hydrogen atom, both of which are hydrogen atoms, or it is more preferable that R ³ is a phosphate group and R ⁴ is a hydrogen atom.
Examples of the compound represented by the general formula (2) include phosphonic acid and diphosphoric acid, and diphosphoric acid is particularly preferable.

In the compound represented by the general formula (3), R ⁵ is preferably a hydroxyl group or a hydrocarbon group having 1 to 18 carbon atoms, more preferably a hydroxyl group or a hydrocarbon group having 1 to 12 carbon atoms.
Examples of the compound represented by the general formula (3) include p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid and the like, and p-toluenesulfonic acid is particularly preferable.

The above specific acids may be used alone or in combination of two or more. Moreover, the said specific acid may use a commercial item, and may manufacture it by a well-known method.

The total content of the saturated aldehyde and the specific acid in the composition of the present invention can be appropriately set according to the use mode. The total content may be 0.1% by mass or more, 10% by mass or more, 30% by mass or more, 50% by mass or more, and 80% by mass. The above may be sufficient and 100 mass% may be sufficient. The total content may be 90% by mass or less, 60% by mass or less, 30% by mass or less, or 5% by mass or less.

The ratio of the content of the saturated aldehyde and the specific acid in the composition of the present invention is usually A: B = 0.0 when the saturated aldehyde is A (parts by mass) and the specific acid is B (parts by mass). 1: 99.9 to 99.9: 0.1, preferably A: B = 5: 95 to 99.9: 0.1, more preferably A: B = 10: 90 to 99.9. From the viewpoint of cost effectiveness, preferably A: B = 20: 80 to 99.5: 0.5, more preferably A: B = 40: 60 to 99: 1. More preferably, A: B = 55: 45 to 99: 1.

The composition of the present invention includes a surfactant, corrosion inhibitor, oxygen scavenger, iron control agent, crosslinking agent, breaker, flocculant, temperature, as long as the effects of the present invention are not impaired, other than saturated aldehydes and specific acids. Stabilizer, pH adjuster, dehydration adjuster, swelling inhibitor, scale inhibitor, biocide, friction reducer, antifoaming agent, anti-mudging agent, lubricant, clay dispersant, weighting agent, gelling agent, An optional component such as a nitrogen-containing compound may be further included.

The composition of the present invention is a monoalcohol or diol having 1 to 10 carbon atoms such as methanol, ethanol, 2-propanol, ethylene glycol, cyclohexane, toluene, xylene, heavy aromatic naphtha, petroleum distillate, water, etc. A suitable solvent may be included as an optional component.

The production method of the composition of the present invention is not particularly limited. For example, (I) a saturated aldehyde, a specific acid, and, if necessary, the optional component for a liquid to be used with the composition of the present invention. And (II) a specific acid is added to the saturated aldehyde in advance before contacting with the liquid, etc., and further if necessary. A method of adding and mixing an optional component such as the solvent, and (III) mixing a saturated aldehyde, a specific acid, and, if necessary, the optional component in advance before contacting with the liquid or the like. It can manufacture by the method to do.

In the composition of the present invention, a saturated aldehyde and a specific acid may be mixed at the time of contact with at least one of a liquid containing a sulfur-containing compound to be used for the composition of the present invention and a gas. From the viewpoint of ease of handling, etc., the composition is formed in advance before adding it to the liquid to be used with the composition of the present invention as in the above methods (II) and (III). It is preferable.

Although the composition of the present invention is preferably in a liquid state, it is suitably supported on a carrier or the like according to the form used to remove the sulfur-containing compound contained in at least one of the liquid and gas, and powders and granules It is good also as solid state, such as.

In removing the sulfur-containing compound contained in at least one of the liquid and the gas using the composition of the present invention, the composition of the present invention may be brought into contact with at least one of the liquid and the gas. Examples of preferred specific embodiments relating to the method for removing a sulfur-containing compound include: (i) a composition of the present invention in an amount sufficient for removing the sulfur-containing compound, and at least one of a liquid and a gas containing the sulfur-containing compound. (Ii) a method of circulating a gas containing a sulfur-containing compound (for example, hydrocarbon) through a container filled with the composition of the present invention, and (iii) a gas containing a sulfur-containing compound. Examples include a method of spraying the composition in a mist form.

In removing the sulfur-containing compound contained in at least one of the liquid and the gas using the composition of the present invention, the amount of the saturated aldehyde contained in the composition of the present invention is the sulfur-containing compound contained in the liquid or gas. The composition of the present invention may be brought into contact with at least one of a liquid and a gas so that the amount is preferably 0.1 to 5000 parts by mass, more preferably 2 to 1000 parts by mass with respect to 1 part by mass of the compound. . For example, in the method (ii) of circulating a gas containing a sulfur-containing compound to a container filled with the composition of the present invention as described above, with respect to 1 part by mass of the sulfur-containing compound in the total amount of gas to be circulated, What is necessary is just to adjust the usage-amount of the composition of this invention so that the quantity of the saturated aldehyde used may be in the said range. Moreover, when removing the sulfur-containing compound contained in both the gas and the liquid, the total amount of the sulfur-containing compound contained in both the gas and the liquid is defined as 1 part by mass, and the amount of the saturated aldehyde used for this. The amount of the composition of the present invention may be adjusted so that is within the above range.

The temperature at which the composition of the present invention is brought into contact with at least one of a liquid and a gas is not particularly limited, but is preferably in the range of −30 ° C. to 150 ° C., more preferably 0 ° C. to 130 ° C. Is within the range.

After contacting the composition of the present invention with at least one of liquid and gas, the composition after contact and the liquid and gas after contact may be separated as necessary. In particular, as in the method (ii) in which a gas (for example, hydrocarbon) containing a sulfur-containing compound is circulated through a container filled with the composition of the present invention as described above, the composition after contact with the composition after contact This is the case when the gas can be easily separated or when the sulfur-containing compound in the liquid is removed, but the phase separation can be performed between the composition after contact and the liquid after contact. It is also possible to adopt a simple method. By doing in this way, content of the sulfur-containing compound in a liquid or gas can be reduced from the initial amount, and the quality of a liquid or gas can be improved.

The following can be illustrated as a more specific aspect at the time of removing the sulfur-containing compound contained in at least one of a liquid and gas using the composition of this invention. That is, when removing the sulfur-containing compound in water using the composition of the present invention, means such as injecting the composition of the present invention into a water storage tank at a sewage treatment plant or the like can be employed.
Further, when removing sulfur-containing compounds in hydrocarbons using the composition of the present invention, if the hydrocarbon is liquid, its storage tank, pipeline for transportation, distillation for purification It can be added by known means such as pouring into a tower or the like. When the hydrocarbon is a gas, the composition of the present invention is installed so as to contact with the gas as described above, or the gas is passed through an absorption tower filled with the composition of the present invention. be able to.

As mentioned above, although embodiment of this invention was described, this invention is not limited to the said embodiment, All the aspects included in the concept of this invention and a claim are included, and various within the scope of this invention. Can be modified.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

First, various materials used in Examples and Comparative Examples are shown below.
<Aldehyde>
1,9-nonanedial and 2-methyl-1,8-octanedial mixture (NL): synthesized in accordance with the method described in Japanese Patent No. 2857055 (content ratio: 1,9-nonanedial is 76.5) (Mass%, 2-methyl-1,8-octane dial is 13.5 mass%, and other aldehydes are 10 mass%)
1-butanal (butanal): Wako Pure Chemical Industries, Ltd. <Triazine>
1,3,5-tris (2-hydroxyethyl) -2,2,4,4,6,6-hexahydro-s-triazine (MEA triazine): according to the method described in WO 92/01481 Synthesized (purity: 85% by mass)
<Acid>
・ Phosphoric acid: manufactured by Wako Pure Chemical Industries, Ltd. ・ Phosphoric acid (2-ethylhexyl): manufactured by Tokyo Chemical Industry Co., Ltd., monoester (30-50% by mass) and diester (50-70% by mass) Dodecyl: manufactured by Wako Pure Chemical Industries, Ltd., monoester only, oleyl phosphate: manufactured by Tokyo Chemical Industry Co., Ltd., monoester (37-50% by mass) and diester (50-63% by mass), ethyl phosphate: Tokyo Chemical Industry Co., Ltd., monoester (35 to 47% by mass) and diester (53 to 65% by mass) mixture, diphenyl phosphate: Tokyo Chemical Industry Co., Ltd., phosphonic acid: Wako Pure Chemical Industries, Ltd. Diphosphoric acid: Wako Pure Chemical Industries, Ltd., p-toluenesulfonic acid monohydrate (toluenesulfonic acid): Wako Pure Chemical Industries, Ltd., methanesulfonic acid: Wako Pure Industrial Co., Ltd., sulfuric acid: Wako Pure Chemical Industries, Ltd., diethyl oxalate: Tokyo Chemical Industry Co., Ltd., diethyl maleate: Wako Pure Chemical Industries, Ltd., acetic acid: Wako Pure Chemical Industries, Ltd., methyl salicylate : Wako Pure Chemical Industries, Ltd., salicylic acid: Wako Pure Chemical Industries, Ltd., citric acid monohydrate (citric acid): Wako Pure Chemical Industries, Ltd., 2-ethylhexanoic acid: Wako Pure Chemical Industries, Ltd.・ Octanoic acid: Wako Pure Chemical Industries, Ltd. ・ Lactic acid: Wako Pure Chemical Industries, Ltd. <Hydrocarbon>
Kerosene: Wako Pure Chemical Industries, Ltd. <sulfur-containing compound>
・ Hydrogen sulfide-containing nitrogen gas: Taiyo Nippon Sanso Co., Ltd., mixed gas of 1 volume% hydrogen sulfide and 99 volume% nitrogen <others>
Carbon dioxide gas: manufactured by Taiyo Nippon Sanso Corporation, purity> 99.995% by volume
Synthetic artificial seawater: An aqueous solution containing 10% by mass of sodium chloride (manufactured by Wako Pure Chemical Industries, Ltd.) and 10% by mass of calcium chloride (manufactured by Wako Pure Chemical Industries, Ltd.)

Example 1
A composition in which NL and phosphoric acid were mixed so as to have the content ratio shown in Table 1 was prepared, and a sulfur-containing compound removal test was performed by the following method using the composition.
<Sulfur-containing compound removal test>
30 mL of kerosene was added to a 100 mL glass three-necked flask equipped with a magnetic stirrer, gas injection tube, and gas discharge cock, and hydrogen sulfide-containing nitrogen gas was circulated at a flow rate of 50 mL / min from the gas injection tube at 800 rpm. The gas in the three-necked flask was replaced with magnetic stirring. After 1 hour, the flow of the hydrogen sulfide-containing nitrogen gas was stopped and the three-necked flask was sealed, and then the initial hydrogen sulfide concentration in the gas phase portion in the three-necked flask was measured.
Next, 1 g of the above composition as a sulfur-containing compound removing agent was added to the kerosene solution, and then the solution was magnetically stirred at 800 rpm at room temperature to perform a hydrogen sulfide removal reaction.
The hydrogen sulfide concentration in the gas phase in the three-necked flask after 2 hours of reaction was measured, and the hydrogen sulfide removal rate [(hydrogen sulfide concentration in the gas phase after the removal reaction ÷ initial hydrogen sulfide concentration in the gas phase)] × 100 (%)] Was calculated. The results are shown in Table 1.

The hydrogen sulfide concentration in the gas phase was measured using the Kitagawa gas detector tube for hydrogen sulfide (manufactured by Komyo Chemical Co., Ltd.), gas collector AP-20 (manufactured by Komyo Chemical Co., Ltd.), and the analytic barrier bag (Omi Odo Air). -Measured by the following method using Service Co., Ltd.
First, 4 mL of a gas sample was collected from the gas phase portion in the three-necked flask, mixed with 156 mL of air in an analytic barrier bag, and diluted 40 times. This analytic barrier bag is connected to the gas sampler AP-20 equipped with a Kitagawa gas detector tube for hydrogen sulfide, and a diluted sample of 100 mL is sucked into the gas detector tube with AP-20 in one minute. Through. After reading the hydrogen sulfide concentration of the diluted sample from the discoloration of the gas detector tube, the concentration was multiplied by 40 to obtain the hydrogen sulfide concentration in the gas phase in the three-necked flask.

(Example 2)
A composition in which NL and phosphoric acid are mixed so as to have the content ratio shown in Table 1 is prepared, and the composition is used as a sulfur-containing compound remover, and the reaction time of the sulfur-containing compound removal test is from 2 hours. Except for changing to 3 hours, a sulfur-containing compound removal test was conducted in the same manner as in Example 1. The results are shown in Table 1.

(Examples 3 and 4)
A composition in which NL and phosphoric acid were mixed so as to have the content ratio shown in Table 1 was prepared, and this composition was used in the same manner as in Example 1 except that the composition was used as a sulfur-containing compound remover. A sulfur compound removal test was conducted. The results are shown in Table 1.

(Example 5)
A composition in which butanal and phosphoric acid were mixed so as to have the content ratio shown in Table 1 was prepared, and the composition was used in the same manner as in Example 1 except that the composition was used as a sulfur-containing compound remover. A sulfur compound removal test was conducted. The results are shown in Table 1.

(Examples 6 to 16)
A method similar to Example 1 except that a composition in which NL and the acid shown in Table 1 were mixed so as to have the content ratio shown in Table 1 was used, and the composition was used as a sulfur-containing compound remover. Then, a sulfur-containing compound removal test was conducted. The results are shown in Table 1.

(Comparative Example 1)
A sulfur-containing compound removal test was conducted in the same manner as in Example 1 except that NL was used alone as a sulfur-containing compound remover. The results are shown in Table 1.

(Comparative Example 2)
A sulfur-containing compound removal test was conducted in the same manner as in Example 1 except that MEA triazine was used alone as a sulfur-containing compound remover. The results are shown in Table 1.

(Comparative Example 3)
A sulfur-containing compound removal test was performed in the same manner as in Example 1 except that phosphoric acid was used alone as a sulfur-containing compound remover. The results are shown in Table 1.

(Comparative Examples 4 to 10 and 12)
A method similar to Example 1 except that a composition in which NL and the acid shown in Table 1 were mixed so as to have the content ratio shown in Table 1 was used, and the composition was used as a sulfur-containing compound remover. Then, a sulfur-containing compound removal test was conducted. The results are shown in Table 1.

(Comparative Example 11)
A composition in which NL and octanoic acid are mixed so as to have the content ratio shown in Table 1 is prepared, and the composition is used as a sulfur-containing compound remover, and the reaction time of the sulfur-containing compound removal test is from 2 hours. Except for changing to 1 hour, a sulfur-containing compound removal test was conducted in the same manner as in Example 1. The results are shown in Table 1.

 

 

As shown in Table 1, when a composition containing a saturated aldehyde and a specific acid was used as the sulfur-containing compound removing agent (Examples 1 to 16), each of the saturated aldehyde and the specific acid was used alone. Compared to the case of using in (Comparative Examples 1 and 3) and the case where an acid other than the specific acid specified in the present invention is used in combination with a saturated aldehyde (Comparative Examples 4 to 12), It was confirmed that the sulfur compound) can be removed more efficiently.

When the MEA triazine of Comparative Example 2 is used alone as the sulfur-containing compound remover, hydrogen sulfide (sulfur-containing compound) in the liquid and gas can be efficiently removed.
However, as a result of the calcium carbonate precipitation generation test conducted by the following method, it was confirmed that when the MEA triazine of Comparative Example 2 was used alone as a sulfur-containing compound remover, calcium carbonate precipitation was likely to occur. It was.

Hereinafter, the calcium carbonate precipitation generation test in the case where each of the composition prepared in Example 1 and the MEA triazine of Comparative Example 2 is used as a sulfur-containing compound remover will be described.
<Calcium carbonate precipitation test>
First, carbon dioxide gas was circulated at room temperature (20 ° C. ± 5 ° C.) in the synthetic simulated seawater, and dissolved until carbon dioxide was saturated. 20 g of this carbon dioxide saturated synthetic seawater was weighed into a glass sample bottle equipped with a magnetic stir bar.
Next, a 1% by mass aqueous solution of a sulfur-containing compound remover was added to carbon dioxide saturated synthetic simulated seawater in a sample bottle until calcium carbonate was precipitated, and the amount of dripping at the time when precipitation occurred was recorded. The results are shown in Table 1. It shows that precipitation is easy to generate | occur | produce, so that there is little dripping amount until calcium carbonate precipitates.

As a result of the above test, when the sulfur-containing compound remover is the composition of Example 1, precipitation of calcium carbonate does not occur even when 50 g of the carbon dioxide-saturated synthetic seawater is dropped, and a colorless transparent solution state Was kept. From this, it was confirmed that the precipitation of calcium carbonate can be suppressed according to the composition of the present invention.

When the sulfur-containing compound remover is the MEA triazine of Comparative Example 2, the solution of carbon dioxide saturated synthetic seawater becomes cloudy at the time when 2.9 g is dropped with respect to carbon dioxide saturated synthetic seawater, and calcium carbonate is precipitated. It was confirmed that the occurrence was easy to occur.

Claims (10)

A composition for removing a sulfur-containing compound contained in at least one of a liquid and a gas,
The sulfur-containing compound is at least one selected from the group consisting of hydrogen sulfide and a compound containing an —SH group;
The composition comprises a saturated aldehyde and at least one acid represented by any one of the following general formulas (1) to (3).

(In the above formula (1), R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms. In the above formula (2), R ³ represents a hydrogen atom or a phosphate group. R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms, and in the above formula (3), R ⁵ represents a hydroxyl group or a hydrocarbon group having 1 to 24 carbon atoms. The composition according to claim 1, wherein the hydrocarbon group is an alkyl group, an alkenyl group or an aryl group. The ratio of the content of the saturated aldehyde to the acid is as follows: A: B = 0.1: 99.9 to 99.99 when the saturated aldehyde is A (parts by mass) and the acid is B (parts by mass). The composition according to claim 1, which is 9: 0.1. The saturated aldehyde is acetaldehyde, propionaldehyde, butanal, isobutyraldehyde, pentanal, 2-methylbutanal, 3-methylbutanal, hexanal, heptanal, octanal, malondialdehyde, succinaldehyde, 3-methylglutaraldehyde, 1 The at least one selected from the group consisting of 1,6-hexane dial, 1,9-nonane dial and 2-methyl-1,8-octane dial. Composition. The composition according to any one of claims 1 to 4, wherein the saturated aldehyde is a saturated aldehyde having 6 or more carbon atoms. The composition according to any one of claims 1 to 5, wherein each of the liquid and the gas is a hydrocarbon. Each of the liquid and gas is natural gas, liquefied natural gas (LNG), liquefied petroleum gas (LPG), sour gas, dry gas, wet gas, oil field gas, associated gas, tail gas, dimethyl ether, crude oil, naphtha, heavy aroma. Naphtha, gasoline, kerosene, diesel oil, light oil, lubricating oil, heavy oil, heavy oil A, heavy fuel oil C, heavy fuel oil, jet fuel oil, FCC slurry, asphalt, condensate, bitumen, super heavy oil, tar, gas liquefied oil (GTL) ), Coal liquefied oil (CTL), asphaltene, aromatic hydrocarbon, alkylate, base oil, kerogen, coke, black oil, synthetic crude oil, reformed gasoline, isomerized gasoline, recycled heavy oil, residual oil, white oil, raffinate , Wax, biomass fuel, biomass liquefied oil (BTL), biogasoline, bioethanol, Is at least one selected from the group consisting of O ETBE and biodiesel, composition according to any one of claims 1 to 5. A method for removing a sulfur-containing compound contained in at least one of a liquid and a gas,
The sulfur-containing compound is at least one selected from the group consisting of hydrogen sulfide and a compound containing an —SH group;
A method of bringing the composition according to any one of claims 1 to 7 into contact with at least one of the liquid and the gas. The method according to claim 8, wherein the composition and the sulfur-containing compound are contacted in the range of -30 ° C to 150 ° C. Use of the composition according to any one of claims 1 to 7 for removing sulfur-containing compounds contained in at least one of a liquid and a gas,
Use, wherein the sulfur-containing compound is at least one selected from the group consisting of a compound containing hydrogen sulfide and a —SH group.