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    • 专利摘要:
    composition for removing sulfur containing compounds. The present invention relates to a composition capable of safely and efficiently removing a sulfur-containing compound contained in a hydrocarbon, particularly hydrogen sulfide, a compound containing -sh group, or a mixture thereof. there is provided a composition for removing a sulfur-containing compound, the sulfur-containing compound being hydrogen sulfide, a compound containing -sh group or a mixture thereof, the composition containing a dialdehyde having 6 to 16 carbon atoms as an active ingredient.
    公开号:BR112016019998B1
    申请号:R112016019998-7
    申请日:2015-03-11
    公开日:2021-07-13
    发明作者:Junichi Fuji；Ryoko Miyazaki；Takahiro Suzuki
    申请人:Kuraray Co., Ltd；
    IPC主号:
    专利说明:

    Technical Field
    [0001] The present invention relates to a composition for removing, or reducing a concentration, of compounds containing sulfur in hydrocarbons, typically hydrogen sulfide, in compound containing group-SH, or a mixture thereof. In detail, the present invention relates to a composition for removing sulfur-containing compounds (typically hydrogen sulfide) contained in fossil fuels, refined petroleum products, and so on, for example, natural gas, liquefied natural gas, gas acid, crude oil, naphtha, heavy aromatic naphtha, gasoline, kerosene, diesel oil, light oil, FCC slurry, asphalt, oil field concentrates, etc., and to a process for removing sulfur-containing compounds (typically hydrogen sulfide ) using composition. Background of the Invention
    [0002] Hydrocarbons, such as fossil fuels, refined petroleum products, etc., for example, natural gas, liquefied natural gas, acid gas, crude oil, naphtha, heavy aromatic naphtha, gasoline, kerosene, diesel oil, light oil, oil heavy, FCC mud, asphalt, oil field concentrates, etc., often contain sulfur-containing compounds such as hydrogen sulfide or a variety of compounds containing -SH group (typically various mercaptans), etc. Hydrogen sulfide toxicity is well known, and in the industry dealing with fossil fuels or refined petroleum products in order to reduce the hydrogen sulfide content to a safe level, considerable costs and efforts are exerted. For example, as for a pipe gas, whose hydrogen sulfide content does not exceed 4 ppm, a lot of regulation values is required. In addition, hydrogen sulfide and a variety of compounds containing -SH group (typically various mercaptans) tend to be released into a vapor space due to their volatility. In this case, their offensive odors are a problem in storage locations and/or their surrounding locations and through piping and shipping systems used to transport the aforementioned hydrocarbons.
    [0003] From the above points of view, in large scale installations dealing with fossil fuels or refined petroleum products, systems for treating a hydrocarbon fluid or hydrocarbon containing hydrogen sulfide are commonly installed. These systems include an absorption tower coming into contact with a hydrocarbon or hydrocarbon fluid and filled with an alkanol amine, PEG, a hindered amine, etc., which absorbs a sulfur-containing compound, such as hydrogen sulfide, or a variety of compounds containing -SH group (typically various mercaptans), carbon dioxide in some cases, and which are capable of being regenerated and used in the treatment system after absorption.
    [0004] Meanwhile, it has long been known that a triazine is used for removing hydrogen sulfide in a hydrocarbon. However, a defect is involved such that triazine cannot be used unless used under basic conditions (triazine is decomposed under neutral to acidic conditions).
    [0005] It has also been known for a long time that an aldehyde compound is used for removing hydrogen sulfide in a hydrocarbon. Specifically, PTL 1 shows the reaction of an aldehyde compound with hydrogen sulfide, particularly the reaction of an aqueous formaldehyde solution with hydrogen sulfide in an aqueous solution at a pH ranging from 2 to 12. Since then, many reports have been made with regarding the use of an aldehyde compound for the purpose of hydrogen sulfide removal. For example, in PTL 2, a water-soluble aldehyde, such as formaldehyde, glyoxal, glutaraldehyde, etc., is used in the form of an aqueous solution as a removal agent for hydrogen sulfide in a hydrocarbon.
    [0006] In the case where the hydrogen sulfide removing agent which is an aqueous solution is merely added to the hydrocarbon, an improvement from the mixing point of view is demanded. For example, PTL 3 mentions that hydrogen sulfide removal efficiency can be improved by adding an emulsifying agent, such as sorbitan sesquiolate, to the aforementioned aldehyde. In addition, in PTL 4, in order to efficiently remove hydrogen sulfide in heavy oil, the hydrogen sulfide removing agent which is an aqueous solution and the heavy oil are emulsified in an injection system including a static mixer.
    [0007] In addition, in the case of use, as the aforementioned water-soluble aldehyde hydrogen sulfide removing agent in a form of an aqueous solution, there is a concept that equipment corrosion is caused by the presence of an acid organic carboxylic through oxidation of formaldehyde, glyoxal, or glutaraldehyde in the aqueous solution. From this point of view, in PTLs 5 and 6, it is proposed to use together, as a corrosion inhibitor, a phosphate salt, such as LiH2PO4, NaH2PO4, Na2HPO4, KH2PO4, K2HPO4, etc., a phosphate ester, a thiophosphate, a thioamine, or the like.
    [0008] However, it is well known that formaldehyde is a mutagenic substance. In addition, as in the Test Examples described below, glutaraldehyde is toxic and is hardly decomposed, and therefore, these aldehydes involve problems with respect to safety at the time of handling and influence on the environment.
    [0009] Meanwhile, PTL 2 shows use of not only the water-soluble aldehyde mentioned above but also acrolein with greater organicity as the hydrogen sulfide scavenger. At SPE Annual Technical Conference and Exhibition SPE146080, held in Denver, Colorado State, U.S.A. from October 30 to November 2, 2011, an announcement regarding the removal of hydrogen sulfide with acrolein as an active ingredient is also made. However, acrolein is highly toxic and is a compound whose concentration is strictly controlled from the standpoints of occupational safety and environmental safety, and therefore such a problem is involved that attention is required for handling.List of CitationsPatent LiteraturePTL 1: US Patent No. 1,991,765PTL 2: US Patent No. 4,680,127PTL 3: US Patent No. 5,284,635PTL 4: WO 2011/087540 APTL 5: US 2013/090271 APTL 6: US 2013/089460 Literature Non-PatentNPL 1: SPE Annual Technical Conference and ExhibitionSPE146080, 2011; http://dx.doi.org/10.2118/146080-MS Invention Summary Technical Problem
    [00010] As previously mentioned, in order to use the conventionally proposed aqueous solution of a water-soluble aldehyde as the removing agent for hydrogen sulfide contained in a hydrocarbon or a hydrocarbon fluid, it was necessary to disperse the aqueous solution of a soluble aldehyde in water in the hydrocarbon by some means, or to inhibit corrosion to be caused by the aqueous solution per se, and other additives or apparatus have become necessary.
    [00011] Therefore, an object of the present invention is to provide a composition capable of safely and efficiently removing a sulfur-containing compound contained in a hydrocarbon, particularly hydrogen sulfide, a compound containing -SH group, or a mixture thereof. Solution to Problem
    [00012] The present invention is as follows.[1] A composition for removing a sulfur-containing compound from a hydrocarbon, the sulfur-containing compound being hydrogen sulfide, a compound containing -SH group or a mixture thereof: a composition containing a dialdehyde having 6 to 16 carbon atoms as an active ingredient .[two] The composition of [1], where the dialdehyde is 1,9-nonadial and/or 2-methyl-1,8-octanedial.[3] The composition of [1] or [2], where the hydrocarbon which is the object of removal of a sulfur-containing compound is one or more selected from the group consisting of natural gas, liquefied natural gas, acid gas, crude oil, naphtha, aromatic naphtha heavy oil, gasoline, kerosene, diesel oil, light oil, heavy oil, FCC mud, asphalt.[4] A process for removing a sulfur-containing compound from a hydrocarbon including using the composition of any one of [1] to [3], the sulfur-containing compound being hydrogen sulfide, a compound containing -SH group, or a mixture thereof. [5] The process of [4], further including the use of a nitrogen-containing compound.[6] The process of ['4] or [5], where the hydrocarbon is one or more selected from the group consisting of natural gas, liquefied natural gas, acid gas, crude oil, naphtha, heavy aromatic naphtha, gasoline, kerosene, diesel oil, light oil, heavy oil, FCC mud, asphalt and oil field concentrates.[7] The process of any one of [4] to [6], where a use amount of the composition of any one of [1] to [3] is in the range of 1 to 10,000 ppm relative to the mass of the hydrocarbon.[8 ] The process of any one of [4] to [7], where the composition of any one of [1] to [3] and the hydrocarbon are brought into contact with each other at about 20°C to 200°C.[ 9] Use the composition of any one of [1] to [3] for removing a sulfur containing compound that is hydrogen sulfide, a compound containing -SH group, or a mixture thereof, in a hydrocarbon. Advantageous Effects of the Invention
    [00013] In view of the fact that the composition of the present invention includes, as an active ingredient, a dialdehyde having 6 to 16 carbon atoms, for example, 1,9-nonanodial and/or 2-methyl-1,8- octanedial or 3-methyl glutaraldehyde, it excels in the removal performance of a sulfur containing compound, particularly hydrogen sulfide, a compound containing -SH group, or a mixture thereof, in a hydrocarbon. In addition, as compared to other aldehydes which have been used to date as the hydrogen sulfide scavenger, particularly the composition of the present invention including 1,9-nonanedial and/or 2-methyl-1,8-octanedial as a active ingredient is low in toxicity and biodegradable, and therefore, does not adversely affect the environment and is excellent in handling safety and also excellent in heat resistance. Therefore, in hydrocarbon storage, transport, or the like, even through use of the composition of the present invention, equipment corrosion is low. Description of Modalities
    [00014] In this specification, the hydrocarbon that is subject to the use of the present composition may be a gas, a liquid, a solid, or a mixture thereof. Examples typically include fossil fuels, refined petroleum products, and so on, for example, natural gas, liquefied natural gas, acid gas, crude oil, naphtha, heavy aromatic naphtha, gasoline, kerosene, diesel oil, light oil, heavy oil, FCC mud, asphalt, oil field concentrates, etc., and arbitrary combinations thereof. However, the hydrocarbon is not limited to them.
    [00015] In the present invention, the sulfur-containing compound that may be contained in the hydrocarbon and which is subject to removal through the use of the composition of the present invention is hydrogen sulfide, a compound containing -SH group, or a mixture thereof. Here, examples of the compound containing -SH group include sulfur containing compounds classified as a mercaptan represented by a chemical formula "R-SH", for example those where R is an alkyl group, including methyl mercaptan, ethyl mercaptan, propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, isobutyl mercaptan, sec-butyl mercaptan, t-butyl mercaptan, and n-amyl mercaptan; those where R is an aryl group, inclusive of phenyl mercaptan; those where R is an aralkyl group, inclusive of benzyl mercaptan; and the like. However, the sulfur-containing compound is not limited thereto.
    [00016] The composition of the present invention is characterized by containing a dialdehyde having 6 to 16 carbon atoms as an active ingredient. Dialdehyde having 6 to 16 carbon atoms is suitably an aliphatic dialdehyde. Examples include methyl glutaraldehyde, 1,6-hexanedial, ethyl pentanedial, 1,7-heptanedial, methyl hexanedial, 1,8-octanedial, methyl heptanedial, dimethyl hexanedial, ethyl hexanedial, 1,9-nonanedial, methyl octanedial, ethyl heptanedial, 1,10-decanedial, dimethyl octanedial, ethyl octanedial, dodecanedial, hexadecanedial, 1,2-cyclohexane dicarbo aldehyde, 1,3-cyclohexane dicarbo aldehyde, 1,4-cyclohexane dicarbo aldehyde, 1,2-cyclooctane dicarb aldehyde, 1,3-cyclooctane dicarb aldehyde, 1,4-cyclooctane dicarb aldehyde, 1,5-cyclooctane dicarb aldehyde, 4,7-dimethyl-1,2- cyclooctane dicarb aldehyde, 4,7-dimethyl-1,3-cyclooctane dicarb aldehyde, 2,6-dimethyl-1,3-cyclooctane dicarb aldehyde, 2,6-dimethyl-1,4-cyclooctane dicarb aldehyde, 2,6-dimethyl-1,5-cyclooctane dicarb aldehyde, octahydro-4,7-methane-1H-indene-2,5-dicarb aldehyde, and the like. Of these, 3-methyl glutaraldehyde, 1,9-nonanedial, and 2-methyl-1,8-octanedial are preferred. From the viewpoint that the composition of the present invention can be provided with low toxicity, biodegradability, handling safety, thermal resistance, and so on, it is more preferred that the composition of the present invention contain at least one of 1, 9-nonanodial and 2-methyl-1,8-octanedial as an active ingredient.
    [00017] In the case where the composition of the present invention contains at least one of 1,9-nonanodial and 2-methyl-1,8-octanodial as an active ingredient, although the active ingredient may be only 1,9-nonanodial or only 2-methyl-1,8-octanedial, from the standpoint of ease of industrial availability, the active ingredient is especially preferably a form of a mixture of 1,9-nonanedial and 2-methyl-1,8-octanedial. Although the mixing ratio of such a mixture of 1,9-nonanedial and 2-methyl-1,8-octanedial is not particularly limited, in general, the mass ratio of 1,9-nonanedial and 2-methyl-1. 8-octanedial is preferably 99/1 to 1/99, more preferably 95/5 to 5/95, even more preferably 90/10 to 45/55, and especially preferably 90/10 to 55/45.
    [00018] All of 1,9-nonanedial and 2-methyl-1,8-octanedial are known substances and can be produced by a process that is known per se (for example, processes described in Japanese patent No. 2857055, JP 62-61577 B, and the like) or proceedings thereunder. In addition, commercially available products can also be used. 3-methyl glutaraldehyde (MGL) is a known substance, too, and can be produced by a known process (eg processes described in Organic Syntheses, Vol. 34, p. 29 (1954) and Organic Syntheses, Vol. 34, p.71 (1954), and the like) or processes therein.
    [00019] 1,9-nonanodial and/or 2-methyl-1,8-octanodial has/has a sterilizing action equal to or greater than glutaraldehyde, is/is low in oral toxicity, excellent in biodegradability, high in safety, and excellent in thermal resistance, and has/has stability in storage.
    [00020] A proportion in content of the dialdehyde that is an active ingredient in the composition of the present invention can be properly fixed according to the mode of use and is generally 1 to 100% by mass. From the point of view of cost performance, the dialdehyde content ratio is preferably 5 to 100% by mass, and more preferably 5 to 95% by mass.
    [00021] The production process of the composition of the present invention is not particularly limited, and a process that is known per se or a process conforming to it can be adopted. The composition of the present invention can be, for example, produced by a process in which a dialdehyde, suitably at least one selected from 3-methyl glutaraldehyde, 1,9-nonandial, and 2-methyl-1,8-octanedial, and especially suitably a mixture of 1,9-nonanedial and 2-methyl-1,8-octanedial is added and mixed with an arbitrary component as described below, if desired, or other procedure.
    [00022] Although the composition of the present invention is suitably a liquid, it can also be a solid, such as a powder, a granule, etc., in a form to be properly supported on a carrier or the like, depending on the form to be used to remove the sulfur-containing compound from the hydrocarbon.
    [00023] In the process of removing compound containing sulfur in the hydrocarbon with the composition of the present invention, in addition to the composition of the present invention, an aldehyde compound that is previously known as the hydrogen sulfide removal agent, such as formaldehyde , glyoxal, glutaraldehyde, acrolein, etc., can be properly added and used.
    [00024] In addition, in the process of removing compound containing sulfur in the hydrocarbon with the composition of the present invention, a compound containing nitrogen can still be added within the range where the effect of the present invention is much more improved or not impaired. Examples of such a nitrogen-containing compound include α-amino ether compounds such as N,N'-oxy bis(methylene)-bis(N,N-dibutyl amine), N,N'-(methylene bis(oxy)bis (methylene))bis(N,N-dibutyl amine), 4,4'-oxy bis(methylene) dimorpholine, bis(morpholino methoxy) methane, 1,1'-oxy bis(methylene) dipiperidine, bis(piperidino methoxy) methane, N,N'-oxy bis(methylene) bis(N,N-dipropyl amine), N,N'-(methylene bis(oxy) bis(methylene)) bis(N,N-dipropyl amine), 1, 1'-oxy bis(methylene) dipyrrolidine, bis(pyrrolidine methoxy) methane, N,N'-oxy bis(methylene)bis(N,N-diethyl amine), N,N'-(methylene bis(oxy) bis( methylene)) bis(N,N-diethyl amine), etc.; alkoxy hexahydro triazine compounds, such as 1,3,5-trimethoxy propyl hexahydro-1,3,5-triazine, 1,3,5-trimethoxy ethyl hexahydro-1,3,5-triazine, 1,3,5-tris( 3-ethoxy propyl) hexahydro-1,3,5-triazine, 1,3,5-tri(3-isopropoxy propyl) hexahydro-1,3,5-triazine, 1,3,5-tri(3-butoxy propyl) ) hexahydro-1,3,5-triazine, 1,3,5-tri(5-methoxy pentyl) hexahydro-1,3,5-triazine, etc.; alkyl hexahydro triazine compounds, such as 1,3,5-trimethyl hexahydro-1,3,5-triazine, 1,3,5-triethyl hexahydro-1,3,5-triazine, 1,3,5-tripropyl hexahydro-1,3,5-triazine, 1,3,5-tributyl hexahydro-1,3,5-triazine, etc.; hydroxy alkyl hexahydro triazine compounds, such as 1,3,5-tri(hydroxy methyl) hexahydro-1,3,5-triazine, 1,3,5-tri(2-hydroxy ethyl) hexahydro-1,3, 5-triazine, 1,3,5-tri(3-hydroxy propyl) hexahydro-1,3,5-triazine, etc.; mono amine compounds such as mono methyl amine, mono ethyl amine, dimethyl amine, dipropyl amine, trimethyl amine, triethyl amine, tripropyl amine, mono methanol amine, dimethanol amine, trimethanol amine, diethanol amine, triethanol amine, mono isopropanol amine, dipropanol amine, diisopropanol amine, tripropanol amine, N-methyl ethanol amine, dimethyl (ethanol) amine, methyl diethanol amine, dimethyl amino ethanol, ethoxy ethoxy ethanol t-butylamine, etc.; diamine compounds, such as amino methyl cyclopentyl amine, 1,2-cyclohexane diamine, 1,4-butane diamine, 1,5-pentane diamine, 1,6-hexane diamine, bis(t-butylamino ethoxy) ethane , etc.; imine compounds; imidazoline compounds; hydroxy amino alkyl ether compounds; morpholine compounds; pyrrolidone compounds; piperidone compounds; alkyl pyridine compounds; 1H-hexahydro azepine; reaction products between an alkylene polyamine and formaldehyde, such as a reaction product between ethylene diamine and formaldehyde, etc.; polyvalent metal chelate compounds of an amino carboxylic acid; quaternary ammonium salt compounds such as benzyl (coco alkyl) (dimethyl) quaternary ammonium chloride, di(coco alkyl) dimethyl ammonium chloride, di(tallow alkyl) dimethyl quaternary ammonium chloride, di(tallow hydroge- nated alkyl) dimethyl quaternary ammonium, dimethyl(2-ethyl hexyl) methyl sulfate (tallow alkyl) ammonium, methyl sulfate (hydrogenated tallow alkyl) (2-ethyl hexyl) dimethyl quaternary ammonium, etc.; polyethylene imine, polyallyl amine, polyvinyl amine; amino carbinol compounds; aminal compounds, bis oxazolidine compounds; and the like. These compounds can be used alone or in combination of two or more of them.
    [00025] In the case where such a compound containing nitrogen is added to the hydrocarbon, there is a concept that NOx is generated in refining, hence applying a charge to the environment. Taking this issue into consideration, it is most preferred that nitrogen containing compost is not added.
    [00026] As an example of preferred embodiments of the present invention, the treatment is carried out by adding the composition of the present invention in an amount sufficient to obtain removal of the sulfur-containing compound (hydrogen sulfide, a compound containing -SH group, or a mixture of them). In the process of removing sulfur-containing compound from the hydrocarbon with the composition of the present invention, in general, the composition of the present invention is added in an amount preferably ranging from 1 to 10,000 ppm relative to the mass of the hydrocarbon. A temperature at which the composition of the present invention is added to, and contacted with, the hydrocarbon for the treatment modality is preferably in the range of 20°C to 200°C. In addition, the composition of the present invention can be used by being dissolved in an appropriate solvent, such as toluene, xylene, heavy aromatic naphtha, petroleum distillate; a mono alcohol or diol having 1 to 10 carbon atoms, for example methanol, ethanol, ethylene glycol, polyethylene glycol, etc.
    [00027] In the process of removing sulfur-containing compound in the hydrocarbon with the composition of the present invention, in the case where the hydrocarbon is a liquid, the composition of the present invention can be added through known processes, such as pouring into a storage tank , a pipeline for transport, a distillation tower for refining, etc., or the like. In the case where the hydrocarbon is a gas, means, for example, installing the composition of the present invention in order to bring it into contact with a gas, allowing the gas to pass through an absorption tower filled with the composition of the invention, or the like , can be taken. Examples
    [00028] The present invention is hereinafter described in more detail with reference to Examples and so on, but it should not be construed so that the present invention is limited to these Examples.<Production Example 1>[Mixture production of 1,9-nonanedial (NL) and 2-methyl-1,8-octanedial (MOL)]
    [00029] A mixture of 1,9-nonanedial (hereinafter referred to as NL) and 2-methyl-1,8-octanedial (hereinafter referred to as MOL) was produced according to a process described in Japanese patent No. 2857055. A mass ratio of NL and MOL in the mixture was NL/MOL = 85/15.<Production Example 2>[Production of 3-methyl glutaraldehyde (MGL)]
    [00030] A 3-methyl glutaraldehyde compound (hereinafter referred to as MGL) was produced according to a procedure described in the literature (Organic Syntheses, Vol. 34, p. 29 (1954)). From the standpoint of stability, this compound was diluted in a form of a 50% by mass aqueous solution and stored.<Example 1>
    [00031] In a three-neck flask having a capacity of 300 mL and equipped with a thermometer, a dropping funnel, and a three-way stopcock, 4.40 g (50 mmoles) of iron sulfide (manufactured by Wako Pure Chemical Industries, Ltd.) were charged, and 50.0 g (100 mmoles) of a 20% aqueous solution of sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise from a dropping funnel at 21°C. °C in 120 minutes, thereby generating hydrogen sulfide.
    [00032] Meanwhile, in a three-neck flask having a capacity of 5 L and equipped with a thermometer and a three-way stopcock, the inside of which was purged with nitrogen, 500 g of kerosene (manufactured by Wako Pure Chemical Industries , Ltd.) were charged and held at 21°C, and the hydrogen sulfide generated above was blown through a three-way stopcock, thereby absorbing onto the kerosene. Next, the three-necked flask was hermetically sealed and allowed to stand at the same temperature for 60 minutes, thus yielding the hydrogen sulfide in an equilibrium state between the liquid phase and the gaseous phase. Next, a concentration of hydrogen sulfide in the gas phase inside the three-neck flask was measured according to a hydrogen sulfide measurement procedure as described later and found to be 510 ppm.
    [00033] The mixture of NL/MOL = 85/15 obtained in Production Example 1 was added to kerosene which was placed in an equilibrium state between liquid phase and gas phase inside the three-neck flask by blowing hydrogen sulfide and absorption of the same there, at a concentration of 850 ppm in relation to the mass of kerosene, and immediately thereafter, the contents were stirred at 21°C under hermetic sealing at 400 rpm. The concentration of hydrogen sulfide in the gas phase inside the flask was measured in the same way as described above at an elapsed time of 60 minutes, 90 minutes, and 120 minutes, respectively, after the addition of NL/MOL. The results are shown in Table 1. It is noted that the concentration of hydrogen sulfide in the gas phase inside the three-neck flask was noticeably reduced. <Hydrogen Sulfide Measurement Process>
    [00034] Using a Kitagawa gas detector tube system (manufactured by Komyo Rikagaku Kogyo KK; used by installing a "120-ST" hydrogen sulfide gas detector tube in an "AP- 20"), 50 mL of a part of the gas phase from the interior of the vial was sampled, and a concentration value in the detector tube was defined as a gas phase hydrogen sulfide concentration. Table 1: Hydrogen sulfide concentration in gas phase
    <Example 2>
    [00035] In a 100 mL autoclave equipped with a thermometer and an agitator, 30 mL of a crude oil collected in Japan was loaded and stirred until a concentration of one part gas phase became constant. Next, the concentration was measured with RX-517 (manufactured by Riken Kiki Co., Ltd.) and found to be 2800 ppm. Subsequently, a liquid composition prepared by mixing PEG-200 and NL/MOL in a molar ratio of 1/1 was added at a concentration of 1% by mass relative to the crude oil. At this time, the amount of addition of NL/MOL was 0.6 mmol, and the amount of presence of H2S inside the apparatus was 0.05 mmol. Next, the interior of the apparatus was subjected to a temperature increase to 80°C while stirring at 800 rpm, and the contents were left to react for 5 hours. After the reaction, the reaction mixture was cooled to room temperature, and the H2S concentration of the gas phase part was measured and found to be 2 ppm, and a removal efficiency was 99.9%.<Example 3>
    [00036] In a 100 mL autoclave equipped with a thermometer and a stirrer, 30 ml of a crude oil collected in Japan was loaded and stirred until the H2S concentration of one part of the gas phase became constant. Next, the concentration was measured with RX-517 (manufactured by Riken Kiki Co., Ltd.) and found to be 2580 ppm. Subsequently, an aqueous solution of MGL 50% by mass was added at a concentration of 1% by mass relative to the crude oil. At this time, the amount of MGL addition was 0.9 mmoles, and the amount of H2S presence inside the apparatus was 0.05 mmoles. Next, the interior of the apparatus was subjected to a temperature rise to 80°C while stirring at 800 rpm, and the contents were left to react for 5 hours. After the reaction, the reaction mixture was cooled to room temperature, an H2S concentration of the gas phase part was measured and found to be 70 ppm, and a removal efficiency was 97.3%.< Comparative Example 1 >
    [00037] In a 100 mL autoclave equipped with a thermometer and a stirrer, 30 mL of a crude oil collected in Japan was loaded and stirred until the H2S concentration of a part of the gas phase became constant. Next, the concentration was measured with RX-517 (manufactured by Riken Kiki Co., Ltd.) and found to be 2714 ppm. Subsequently, an aqueous solution 50% by mass of glutaraldehyde was added at a concentration of 1% by mass relative to the crude oil. At this moment, the amount of addition of glutaraldehyde was 1.0 mmol, and the amount of presence of H2S inside the appliance was 0.05 mmoles. Next, the interior of the apparatus was subjected to a temperature increase to 80°C while stirring at 800 rpm, and the contents were left to react for 5 hours. After the reaction, the reaction mixture was cooled to room temperature, an H2S concentration of the gas phase part was measured and found to be 100 ppm, and a removal efficiency was 96.3%.< Comparative Example 2 >
    [00038] In a 100 mL autoclave equipped with a thermometer and an agitator, 30 mL of a crude oil collected in Japan was loaded and stirred until a H2S concentration of a part of the gas phase became constant. Next, the concentration was measured with RX-517 (manufactured by Riken Kiki Co., Ltd.) and found to be 2600 ppm. Subsequently, a 40% by mass aqueous solution of glyoxal (manufactured by Wako Pure Chemical Industries, Ltd.) was added at a concentration of 1% by mass relative to the crude oil. At this time, the amount of glyoxal addition was 1.8 mmoles, and the amount of H2S presence inside the apparatus was 0.04 mmoles. Next, the interior of the apparatus was subjected to a temperature increase to 80°C while at 800 rpm, and the contents were left to react for 5 hours. After the reaction, the reaction mixture was cooled to room temperature, and H2S concentration of the gas phase part was measured and verified to be 498 ppm, and a removal efficiency was 80.8%.< Test Example 1 >
    [00039] With respect to NL, MOL, and glutaraldehyde, measurement of oral toxicity, toxicity test on algae, bactericidal test on mud, and biodegradability test were performed. The testing processes and results are as follows.< Oral Toxicity >
    [00040] A test substance that was emulsified and dispersed in a 2% aqueous solution of gum arabic (containing 0.5% - Tween 80) was compulsorily administered to a 6-week-old male CRj:CD(SD) rat once per day for 14 days through the use of an oral gavage. A variation in body weight and general condition during the administration period were observed. The rat was fasted for one day from the date of final administration (drink was taken freely), and on the day after final administration, taking a blood sample (for various blood tests) and major organ mass measurements were performed. . In addition, with respect to liver, kidney, spleen, and testes, a histopathological examination (optical microscopic observation of a thin piece of tissue stained with HE) was also performed. One dose was set at 1000, 250, 60, 15, and 0 mg/kg/day (net volume of administration = 1 mL/100g body weight/day), respectively, and five animals were used for each dose. Tests: (1) NL (GC purity: 99.7%) (2) Glutaraldehyde (water content: 101 ppm, GC purity: 99.8%)
    [00041] As a test result, with respect to NL, no fatal cases were admitted even at the highest dose of 1000 mg/kg/day. NL does not correspond to a "harmful substance". A maximum no-effect level (NOEL) under the present test conditions is shown in Table 2. Table 2: Oral toxicity test results
    < Algae Test >
    [00042] An algal growth inhibition test of a test substance was performed with reference to OECD Test Guidelines No. 201. That is, each of the following test substances was diluted with a test medium to a prescribed dosage. A liquid suspension of algae that had been grown to an exponential growth phase by pre-culture was added at an initial concentration of 1x104 cells/ml. The liquid suspension was cultured with agitation at 23°C using a light irradiation type bioagitator (BR-180LF, manufactured by Taitec Corporation), the number of algal cells in an elapsed time of 24, 48, and 72 hours, respectively after the start of the test was counted with a flow cytometer (Cell Lab Quant SC, manufactured by Beckman Coulter, Inc.), and a growth rate at each test dose was calculated while setting the normal control growth rate to 100 %. In addition, ErC50 was calculated according to an approximate curve equation of a graph plotting a growth inhibition ratio. Potassium dichromate was used as a standard substance.Algae: Pseudokirchneriella subcapitata Test Substances:(1) Mixture of NL and MOL (GC purity: 98.7%, NL/MOL = 59/41)(2) Glutaraldehyde (water content: 101 ppm, GC purity: 99.8%) Test substance dosage:
    [00043] Each of the test substance (1) and the test substance (2): 100, 32, 10, 3.2, 1, 0.32 mg/L (common ratio: ^10, and 0 mg/L ( normal control)
    [00044] Standard Substance: 3.2, 1, 0.32 mg/L, and 0 mg/L (normal control)
    [00045] In the present test, in view of the fact that the ErC50 of potassium dichromate (standard substance) at an elapsed time of 72 hours was 1.3 mg/L, and the growth rate of the normal control in an elapsed time of 72 hours was 93.0%, it was concluded that the present test was operated normally. Test results are shown in Table 3.Table. Algae toxicity test results
    < Mud Bactericide Test >
    [00046] To a synthetic sewage water prepared by dissolving 5 g each of glucose, peptone and mono potassium dihydrogen phosphate in one liter of water and adjusting the pH to 7.0 +/- 1.0 with sodium hydroxide sodium, a sludge from the dump treatment facility located in Mizushima District, Kurashiki-shi, Okayama Prefecture, Japan was added in an amount of 30 ppm as converted to dry mass, thereby preparing a bacterial culture. Meanwhile, a test substance was diluted with distilled water on a scale of one to ten to a final concentration of 1000 to 0.004 ppm (common ratio = 4) on a 24-well microplate, thereby preparing test solutions. Two wells were used for any concentration. As a comparison target, (distilled water + bacterial culture) was defined as "bacterial culture blank", and distilled water alone was defined as "white".
    [00047] The bacterial culture prepared above and test solution were mixed at a volume ratio of 1/1, and the mixture was left to stand inside a thermostatic tank at room temperature (about 25°C) for 24 hours and 48 hours, respectively. A level of sludge influence at each concentration of test substance was visually observed by means of the MTT process. An MTT reagent is converted by mitochondria as a microorganism in the mud to form formazan, thereby developing a blue color. In the case where the microorganism dies, the previous reaction does not occur, and the reagent shows yellow. Test substances: (1) Mixture of NL and MOL (GC purity: 98.7%, NL/MOL = 59/41 (2) Glutaraldehyde (water content: 101 ppm, GC purity: 99.8%)
    [00048] The results are shown in Table 4.Table 4: Results of bactericidal test on mud
    < Biodegradability Test >
    [00049] A test substance biodegradability test has been carried out with reference to the test processes of OECD Test Guidelines 301C and JIS K6950 (ISO 14851). That is, 300 mL of a solution of inorganic medium and 9 mg (30 ppm) of activated sludge obtained on the day of the start of the test from the waste treatment facility located in Mizushima District, Kurashiki-shi, Okayama Prefecture, Japan, were loaded into a culture bottle. In view of the fact that both test substances have a sterilizing action, an influence on the sludge was considered, and a biodegradability test was carried out at two concentrations of a high concentration group: 30 mg (100 ppm) of test substance and one low concentration group: 9 mg (30 ppm) of test substance. Test Substances: (1) Mixture of NL and MOL (GC purity: 98.7%, NL/MOL = 59/41) (2) Glutaraldehyde (content of water: 101 ppm, GC purity: 99.8%)
    [00050] After culture using a coulometer (type 3001A, manufactured by Ohkura Electric Co., Ltd.) at 25oC for 28 days, a biodegradation rate was calculated from an amount of oxygen consumed for the decomposition of the test substance and a theoretical oxygen demand determined from a structural formula of the test substance. As a standard biodegradable substance, 30 mg (100 ppm) of aniline was used. When the biodegradation ratio was 60% or more, the test substance was decided to be a good degradable substance. The test substance evaluation number was n = 2.
    [00051] As a result of measurement under the above conditions, aniline as a standard biodegradable substance showed a biodegradation rate of 60% or more during the test period and was decided to have good degradability. Accordingly, it was concluded that the present test system was operated normally.
    [00052] The biodegradation ratio of the high concentration NL/MOL group (100 ppm) for 28 days was 88.4% and 86.8%, respectively (mean: 87.6%), and the group was decided have "good degradability".
    [00053] The biodegradation ratio of the low NL/MOL (30 ppm) group for 28 days was 100.3% and 97.3%, respectively (mean: 98.8%), and the group was decided to have "good degradability".
    [00054] The biodegradation ratio of the high concentration glutaraldehyde (100 ppm) group for 28 days was 52.7% and 52.5%, respectively (mean: 52.6%), and the group was decided to have "degradability partial (hardly degradable)".
    [00055] The biodegradation ratio of the low glutaraldehyde (30 ppm) group for 28 days was 78.5% and 77.5%, respectively (mean: 78.0%), and the group was decided to have " good degradability".
    [00056] From the above results, NL and/or MOL has/has low oral toxicity as compared to glutaraldehyde, the toxicity test results on algae are good, and the biodegradability is high. Likewise, it is noted that NL and/or MOL are/is high in safety from the point of view of environmental and occupational safety as compared to glutaraldehyde. < Example Test 2 >< Thermal Stability Test >
    [00057] A vial bottle was loaded with each of the following test solutions, a part of the air space of which was then purged with nitrogen, and hermetically sealed, followed by storage at 60oC. When an NL/MOL or glutaraldehyde content of each test solution immediately after the start of storage was set to 100%, a change in content within an elapsed time of 5 days, 12 days, and 21 days, respectively, was observed according to a calibration curve by means of gas chromatography with an internal standard. The results are shown in Table 5. Test Solution 1: Mixture of NL and MOL (mass ratio: 92/8) Test Solution 2: Mixture of NL/MOL/water = 91/7/2 (mass ratio) Test Solution 3 : 50% glutaraldehyde aqueous solution (manufactured by Tokyo Chemical Industry Co., Ltd.)[Gas Chromatography Analysis Conditions]Analysis Instrument: GC-14A (manufactured by Shimadzu Corporation)Detector: FID (Flame Flame Ionization Detector) hydrogen)Column used: G-300 (length: 20 m, film thickness: 2 micrometers, inner diameter: 1.2 mm) (manufactured by Chemicals Evaluation and Research Institute, Japan)Analysis conditions: 250oC injection temperature, 250oC injection temperature detection 250oC Temperature rise conditions: 80oC -> (temperature rise in 5oC/minute) -> 230oC Internal standard substance: diglyme (diethylene glycol dimethyl ether) Table 5: Thermal stability test results
    Calculated based on content on day 0 as 100%
    [00058] In test solution 1 and test solution 2 each containing NL and MOL, 98% remained even after 21 days. On the other hand, in test solution 3 containing glutaraldehyde, the remaining amount was 62% after 21 days.
    [00059] Likewise, it is noted that NL and/or MOL are/is greater in thermal stability than aqueous glutaraldehyde solution.< Test Example 3 >
    [00060] In order to evaluate the corrosion capacity of an aqueous solution of aldehyde on metals, the following aqueous solutions were prepared.A: 1% aqueous solution of NL/MOL prepared by diluting a mixture of NL/MOL with distilled waterB : 1% aqueous MGL solution prepared by diluting MGL with distilled waterC: 1% aqueous glutaraldehyde solution prepared by diluting a 50% aqueous glutaraldehyde solution (manufactured by Wako Chemical Industries, Ltd) with distilled waterD: aqueous solution 1% glyoxal prepared by diluting a 40% aqueous glyoxal solution (manufactured by Tokyo Chemical Industry Co., Ltd) with distilled water E: distilled water (white)
    [00061] Five 50 mL threaded tubes were loaded with a test piece of SS400 (20 mm x 20 mm x 2 mm) and 25 g of each of the aqueous solutions of aldehyde A to D at atmospheric pressure, hermetically sealed, and then stored inside a circulation-type dryer set at 85oC for 9 days. After storage ended, the test piece was removed, and an iron ion concentration in the aqueous solution was measured through the atomic absorption process. The results are shown in Table 6.< Example Test 4 >
    [00062] The same procedures as in Test Example 3 were followed to measure a concentration of iron ion in each of the aqueous solutions, except that in Test Example 3, the hermetic sealing was carried out under nitrogen. The results are shown in Table 6.Table 6: Corrosion Capacity Test Results

    [00063] From the results of Test Example 3 and Test Example 4, it is noted that in the aqueous solution of NL/MOL and the aqueous solution of MGL, iron corrosion is inhibited as compared to the aqueous solution of glutaraldehyde and the solution aqueous glyoxal.
    权利要求:
    Claims (5)
    [0001]
    1. Process for removing a sulfur-containing compound from a hydrocarbon, characterized in that it comprises using a composition comprising 1,9 nonanodial and/or 2-methyl-1,8-octanedial, or 3-methyl glutaraldehyde, as an ingredient active, the sulfur-containing compound being hydrogen sulfide, a compound containing -SH group, or a mixture thereof.
    [0002]
    2. Process according to claim 1, characterized in that it further comprises the use of a nitrogen-containing compound.
    [0003]
    3. Process according to claim 1 or 2, characterized in that the hydrocarbon is one or more selected from the group consisting of natural gas, liquefied natural gas, acid gas, crude oil, naphtha, heavy aromatic naphtha, gasoline, kerosene , diesel oil, light oil, heavy oil, FCC mud, asphalt, and oil field concentrates.
    [0004]
    4. Process according to any one of claims 1 to 3, characterized in that an amount of use of the composition is in the range of 1 to 10,000 ppm in relation to the mass of the hydrocarbon.
    [0005]
    5. Process according to any one of claims 1 to 4, characterized in that the composition and the hydrocarbon are placed in contact with each other at 20°C to 200°C.
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    同族专利:
    公开号 | 公开日
    CA2942276C|2021-12-14|
    MX2016011811A|2017-03-14|
    CN106103659B|2018-07-06|
    US10119079B2|2018-11-06|
    TW201540653A|2015-11-01|
    EP3121251A1|2017-01-25|
    SG11201607665RA|2016-10-28|
    CN106103659A|2016-11-09|
    EP3121251B1|2019-05-08|
    US20170081597A1|2017-03-23|
    JP6446029B2|2018-12-26|
    WO2015141535A1|2015-09-24|
    RU2016136673A|2018-04-19|
    JPWO2015141535A1|2017-04-06|
    TWI643810B|2018-12-11|
    BR112016019998A2|2017-08-15|
    RU2016136673A3|2018-08-29|
    EP3121251A4|2017-10-25|
    KR20160135191A|2016-11-25|
    RU2687079C2|2019-05-07|
    CA2942276A1|2015-09-24|
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    法律状态:
    2019-12-31| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-11-24| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2021-05-25| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-07-13| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 11/03/2015, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2014053181|2014-03-17|
    JP2014-053181|2014-03-17|
    PCT/JP2015/057114|WO2015141535A1|2014-03-17|2015-03-11|Composition for removal of sulphur-containing compounds|
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