Triazine formulation solvent for deodorization and use thereof

Abstract

The application discloses a triazine formula solvent for deodorization and application thereof, and the triazine formula solvent comprises the following components: 1,3,5-tri(2-hydroxyethyl)-hexahydro-sym-triazine and a synergist; the synergist comprises dithiothiophene dioxide and piperazine. The triazine compound is selected from 1,3,5-tri(2-hydroxyethyl)-hexahydro-sym-triazine, dithiothiophene dioxide and piperazine are combined to be used as the synergist, the overall desulfurization effect of the triazine formula solvent is greatly improved, the sulfur capacity is improved, and the removal efficiency of hydrogen sulfide and methyl mercaptan is improved. The application is suitable for gas field water flash gas desulfurization.

Description

Technical Field

[0001] This invention belongs to the field of gas processing technology, specifically relating to a triazine formulation solvent for deodorization and its application. Background Technology

[0002] The main components of flash steam from gas fields are hydrogen sulfide, carbon dioxide, and methane. Hydrogen sulfide concentration can reach as high as 300 g / m³, while the potential sulfur content is mostly below 30 kg / d. Hydrogen sulfide is the primary odor control factor and requires purification before discharge. Due to the characteristics of low flow rate, high hydrogen sulfide concentration, and low potential sulfur content, gas field flash steam is currently treated using alkaline absorption, solid-state desulfurization, and liquid-phase oxidation-reduction technologies. However, alkaline absorption suffers from carbon dioxide co-absorption and consumption, and the reaction products are prone to saturation and precipitation, leading to blockage. While solid-state desulfurization is relatively simple, it involves high investment. Liquid-phase oxidation-reduction technology also has issues with high investment and slightly lower stability. Therefore, further optimization of the technology for treating gas field flash steam is necessary.

[0003] Triazine compounds are heterocyclic compounds containing three nitrogen atoms, characterized by rapid and selective reaction with hydrogen sulfide. The reaction products of triazine desulfurizers and hydrogen sulfide are water-soluble, have low toxicity, are biodegradable, and can be treated by mixing with produced liquids from gas fields and reinjecting them into the formation.

[0004] However, the desulfurization efficiency of conventional triazine desulfurizers needs further improvement. Furthermore, the inventors have discovered at least the following problems in the prior art: existing triazine desulfurization solutions are prone to precipitation when exposed to high concentrations of hydrogen sulfide, prone to foaming when exposed to high concentrations of carbon dioxide, decompose in acidic environments, and are unable to remove organic sulfur. Summary of the Invention

[0005] The technical problem to be solved by this invention is that the desulfurization efficiency of conventional triazine desulfurizers needs to be further improved. This invention provides a deodorization triazine formulation solvent and its application to solve the above problem, which increases the removal rate of organic sulfur. At the same time, tetrahydrothiophene dioxide and piperazine also have hydrogen sulfide selectivity, reducing the co-absorption consumption of carbon dioxide in the solution.

[0006] This invention is achieved through the following technical solution:

[0007] A triazine formulation solvent for deodorization comprises the following components: 1,3,5-tris(2-hydroxyethyl)-hexahydrotriazine and a synergist; said synergist includes tetrahydrothiophene dioxide and piperazine.

[0008] The triazine compound designed in this invention is 1,3,5-tris(2-hydroxyethyl)-hexahydrotriazine, and tetrahydrothiophene dioxide and piperazine are used as synergists to significantly improve the overall desulfurization effect of the triazine formulation solvent, increase sulfur capacity, and improve the removal efficiency of hydrogen sulfide and methanethiol.

[0009] More preferably, the tetrahydrothiophene dioxide accounts for 8% to 12% of the mass percentage of the formulation solution; and the piperazine accounts for 6% to 10% of the mass percentage of the formulation solution.

[0010] Excessive or insufficient addition of tetrahydrothiophene dioxide and piperazine is detrimental to desulfurization efficiency, and may even reduce sulfur capacity, resulting in poor economic performance. Based on experimental design results, this invention preferably designs the mass percentage of tetrahydrothiophene dioxide in the formulation solution to be 8%–12%, and the mass percentage of piperazine in the formulation solution to be 6%–10%. Within this range, the desulfurization effect on gas field flash steam is optimal.

[0011] More preferably, the tetrahydrothiophene dioxide accounts for 10% of the mass percentage of the formulation solution, and the piperazine accounts for 8% of the mass percentage of the formulation solution.

[0012] More preferably, the 1,3,5-tris(2-hydroxyethyl)-hexahydrotriazine accounts for 40% to 55% of the mass percentage of the formulation solution.

[0013] This invention selects 1,3,5-tris(2-hydroxyethyl)-hexahydrotriazine mixed with two synergists as the main desulfurization active component. When the concentration of 1,3,5-tris(2-hydroxyethyl)-hexahydrotriazine is below 40%, precipitation easily occurs in the solution, and the desulfurization effect is poor. Since H2S is more easily ionized in the aqueous phase, it is more easily absorbed by the desulfurizing agent. Therefore, when the concentration of 1,3,5-tris(2-hydroxyethyl)-hexahydrotriazine is above 55%, the sulfur capacity begins to decrease significantly.

[0014] More preferably, the 1,3,5-tris(2-hydroxyethyl)-hexahydrotriazine accounts for 50% of the mass percentage of the formulation solution.

[0015] Further optimization includes scale inhibitors, defoamers, and pH stabilizers.

[0016] Further preferred, by mass percentage, it includes the following components: 1,3,5-tris(2-hydroxyethyl)-hexahydrotriazine, 40%–55%; tetrahydrothiophene dioxide, 8%–12%; piperazine, 6%–10%; scale inhibitor, 6%–8%; defoamer, 0.1%–0.2%;

[0017] pH stabilizer, 6%–10%; the remainder is water.

[0018] More preferably, the scale inhibitor comprises disodium hydrogen phosphate and phosphoric acid; the defoamer comprises modified silicone oil, such as defoamer KS-604; and the pH stabilizer comprises 2-amino-2-methyl-1-propanol.

[0019] An application of a triazine formulation solvent for deodorization, characterized in that it is used for gas field water flash steam desulfurization; the triazine formulation solvent for deodorization is the aforementioned triazine formulation solvent for deodorization.

[0020] Further preferably, the hydrogen sulfide content in the gas field flash steam is less than 250 g / m³. 3 Carbon dioxide content less than 500g / m³ 3 Methanethiol content less than 30 mg / m³ 3 The potential sulfur content is less than 10 kg / d.

[0021] Further preferably, the hydrogen sulfide content in the gas field flash steam is 140 g / m³. 3 -220g / m 3 Carbon dioxide content 350g / m³ 3 -450g / m 3 Methanethiol content 10mg / m 3 -20mg / m 3 The potential sulfur content is 5 kg / d - 10 kg / d.

[0022] The present invention has the following advantages and beneficial effects:

[0023] 1. This invention provides a triazine formulation solvent for deodorization, using 1,3,5-tris(2-hydroxyethyl)-hexahydrotriazine as the triazine compound, and employing tetrahydrothiophene dioxide and piperazine as synergists. This significantly improves the overall desulfurization effect of the triazine formulation solvent, increasing sulfur capacity and the removal efficiency of hydrogen sulfide and methanethiol. Adding tetrahydrothiophene dioxide and piperazine to the 1,3,5-tris(2-hydroxyethyl)-hexahydrotriazine desulfurization solution increases the removal rate of organic sulfur. Simultaneously, tetrahydrothiophene dioxide and piperazine also exhibit selective desulfurization characteristics, reducing the consumption of carbon dioxide co-absorption in the solution.

[0024] 2. The present invention provides a triazine formulation solvent for deodorization, suitable for gas field flash steam desulfurization, removing hydrogen sulfide and methanethiol from gas field flash steam; particularly suitable for gas field flash steam with a hydrogen sulfide content of less than 250 g / m³. 3 Carbon dioxide content less than 500g / m³ 3 Methanethiol content less than 30 mg / m³ 3 When the potential sulfur content is less than 10 kg / d.

[0025] 3. The triazine formulation solvent for deodorization provided by this invention is prone to precipitation when absorbing high concentrations of hydrogen sulfide, and prone to foaming when encountering high concentrations of carbon dioxide. Furthermore, it easily decomposes under acidic conditions, and is essentially ineffective at removing organic sulfur. This invention incorporates an antifoaming agent to reduce foaming, and adds a scale inhibitor and a pH stabilizer to further reduce precipitation, thereby improving absorption efficiency. This triazine formulation solvent improves the sulfur capacity of the solvent while preventing precipitation in the solution. Detailed Implementation

[0026] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the embodiments. The illustrative embodiments and descriptions of this invention are only for explaining this invention and are not intended to limit this invention.

[0027] In the following description, numerous specific details are set forth in order to provide a thorough understanding of the invention. However, it will be apparent to those skilled in the art that these specific details are not necessary to practice the invention. In other embodiments, well-known structures, materials, or methods have not been specifically described in order to avoid obscuring the invention.

[0028] Throughout this specification, references to “an embodiment,” “an example,” or “an example” mean that a particular feature, structure, or characteristic described in connection with that embodiment or example is included in at least one embodiment of the invention. Therefore, the phrases “an embodiment,” “an example,” “an example,” or “an example” appearing in various places throughout the specification do not necessarily refer to the same embodiment or example. Furthermore, specific features, structures, or characteristics can be combined in one or more embodiments or examples in any suitable combination and / or sub-combination. The term “and / or” as used herein includes any and all combinations of one or more of the associated listed items.

[0029] A specific embodiment provides a triazine formulation solvent for gas field water flash vapor deodorization, which, by mass percentage, comprises:

[0030] 1,3,5-Tris(2-hydroxyethyl)-hexahydrotriazine, 40%–55%;

[0031] Tetrahydrothiophene dioxide, 8%–12%;

[0032] Piperazine, 6%–10%;

[0033] Scale inhibitor, 6%–8%;

[0034] Defoamer, 0.1%–0.2%;

[0035] 2-Amino-2-methyl-1-propanol, 6%–10%;

[0036] The remainder is water.

[0037] The preferred mass percentages of each component in the above triazine formulation solvent are as follows:

[0038] 1,3,5-Tris(2-hydroxyethyl)-hexahydrotriazine, 45%–50%;

[0039] Tetrahydrothiophene dioxide, 10%–11%;

[0040] Piperazine, 7%–8%;

[0041] Scale inhibitor, 6%–7%;

[0042] Defoamer, 0.10%–0.15%;

[0043] 2-Amino-2-methyl-1-propanol, 7%–8%;

[0044] The remainder is water.

[0045] Piperazine and tetrahydrothiophene dioxide are used as synergists; the scale inhibitor is preferably a combination of disodium hydrogen phosphate and phosphoric acid, with disodium hydrogen phosphate accounting for 5% of the mass percentage of the formulation solution and phosphoric acid accounting for 1% of the mass percentage of the formulation solution; the defoamer is preferably KS-604; and the pH stabilizer is preferably 2-amino-2-methyl-1-propanol.

[0046] The hydrogen sulfide content in the flash steam of the gas field is less than 200 g / m³. 3 Carbon dioxide content less than 400g / m³ 3 Methanethiol content less than 15 mg / m 3 The potential sulfur content is 10 kg / d.

[0047] Desulfurization method: Set up an absorption column of DN15×400, two layers of glass sand core filter plates, a packing height of 300mm, 20ml of formulated solvent, and a processing capacity of 4L / h. Conduct a 6h static absorption test at room temperature and pressure. Take 20 sets of data for each test and calculate the average value.

[0048] The specific implementation method is shown below.

[0049] Example 1

[0050] The triazine solvent formulation in this embodiment, calculated by mass percentage, has the following composition:

[0051] 1,3,5-Tris(2-hydroxyethyl)-hexahydrotriazine, 40%;

[0052] Tetrahydrothiophene dioxide, 11%;

[0053] Piperazine, 10%;

[0054] Scale inhibitor, 8%;

[0055] Defoamer, 0.15%;

[0056] 2-Amino-2-methyl-1-propanol, 8%;

[0057] Water, remaining amount.

[0058] The purified gas obtained after the above-mentioned triazine formulation absorbs H2S and methanethiol has an H2S content of 1.15 mg / m³. 3 The methanethiol content is 0.85 mg / m³. 3 The sulfur capacity reaches 95.54 g / L; the solution is clear during the absorption process, gradually turns into a grayish-white suspension as it approaches saturation, turns yellow after standing, and gradually returns to clear and transparent.

[0059] Example 2

[0060] The triazine solvent formulation in this embodiment, calculated by mass percentage, has the following composition:

[0061] 1,3,5-Tris(2-hydroxyethyl)-hexahydrotriazine, 50%;

[0062] Tetrahydrothiophene dioxide, 10%;

[0063] Piperazine, 8%;

[0064] Scale inhibitor, 6%;

[0065] Defoamer, 0.10%;

[0066] 2-Amino-2-methyl-1-propanol, 8%;

[0067] Water, remaining amount.

[0068] The purified gas obtained after the above-mentioned triazine formulation solvent absorbs H2S and methanethiol has an H2S content of 0.21 mg / m³. 3 The methanethiol content is 1.21 mg / m³. 3 The sulfur capacity is 128.98 g / L, and the solution remains clear during absorption without any precipitate.

[0069] Example 3

[0070] The triazine solvent formulation in this embodiment, calculated by mass percentage, has the following composition:

[0071] 1,3,5-Tris(2-hydroxyethyl)-hexahydrotriazine, 55%;

[0072] Tetrahydrothiophene dioxide, 9%;

[0073] Piperazine, 6%;

[0074] Scale inhibitor, 6%;

[0075] Defoamer, 0.10%;

[0076] 2-Amino-2-methyl-1-propanol, 6%;

[0077] Water, remaining amount.

[0078] The purified gas obtained after the above-mentioned triazine formulation solvent absorbs H2S and methanethiol has an H2S content of 0.97 mg / m³. 3 The methanethiol content is 1.23 mg / m³. 3 The sulfur capacity is 103.12 g / L, and the solution is clear during the absorption process without any precipitation.

[0079] Example 4

[0080] The triazine solvent formulation in this embodiment, calculated by mass percentage, has the following composition:

[0081] 1,3,5-Tris(2-hydroxyethyl)-hexahydrotriazine, 45%;

[0082] Tetrahydrothiophene dioxide, 11%;

[0083] Piperazine, 7%;

[0084] Scale inhibitor, 6%;

[0085] Defoamer, 0.10%;

[0086] 2-Amino-2-methyl-1-propanol, 9%;

[0087] Water, remaining amount.

[0088] The purified gas obtained after the above-mentioned triazine formulation solvent absorbs H2S and methanethiol has an H2S content of 0.83 mg / m³. 3 The methanethiol content is 0.96 mg / m³. 3 The sulfur capacity is 118.23 g / L, and the solution remains clear during absorption without any precipitate.

[0089] Example 5

[0090] The triazine solvent formulation in this embodiment, calculated by mass percentage, has the following composition:

[0091] 1,3,5-Tris(2-hydroxyethyl)-hexahydrotriazine, 50%;

[0092] Tetrahydrothiophene dioxide, 9%;

[0093] Piperazine, 8%;

[0094] Scale inhibitor, 7%;

[0095] Defoamer, 0.15%;

[0096] 2-Amino-2-methyl-1-propanol, 8%;

[0097] Water, remaining amount.

[0098] The purified gas obtained after the above-mentioned triazine formulation solvent absorbs H2S and methanethiol has an H2S content of 0.95 mg / m³. 3 The methanethiol content is 1.28 mg / m³. 3 The sulfur capacity is 120.71 g / L, and the solution is clear during the absorption process without any precipitation.

[0099] Comparative Example 1

[0100] The triazine solvent formulation in this comparative case, calculated by mass percentage, has the following composition:

[0101] 1,3,5-Tris(2-hydroxyethyl)-hexahydrotriazine, 50%;

[0102] Scale inhibitor, 6%;

[0103] Defoamer, 0.10%;

[0104] 2-Amino-2-methyl-1-propanol, 8%;

[0105] Water, remaining amount.

[0106] The purified gas obtained after the above-mentioned triazine formulation absorbs H2S and methanethiol has an H2S content of 1.05 mg / m³. 3 The methanethiol content was 11.24 mg / m³. 3 The sulfur capacity reached 73.87 g / L, the solution absorption process was stable, and no precipitation occurred throughout the absorption process. Without the addition of a synergist, the solution sulfur capacity was poor, and organic sulfur was basically not absorbed.

[0107] Comparative Example 2

[0108] The triazine solvent formulation in this comparative case, calculated by mass percentage, has the following composition:

[0109] 1,3,5-Tris(2-hydroxyethyl)-hexahydrotriazine, 50%;

[0110] Tetrahydrothiophene dioxide, 18%;

[0111] Scale inhibitor, 6%;

[0112] Defoamer, 0.10%;

[0113] 2-Amino-2-methyl-1-propanol, 8%;

[0114] Water, remaining amount.

[0115] The purified gas obtained after the above-mentioned triazine formulation solvent absorbs H2S and methanethiol has an H2S content of 1.32 mg / m³. 3 The methanethiol content is 6.12 mg / m³. 3 The sulfur capacity can reach 100.54 g / L, the solution absorption process is stable, and there is no precipitation throughout the absorption process. When only tetrahydrothiophene dioxide is added as a synergist, the sulfur capacity is improved, but the purification effect of organic sulfur still does not meet the standard.

[0116] Comparative Example 3

[0117] The triazine solvent formulation in this comparative case, calculated by mass percentage, has the following composition:

[0118] 1,3,5-Tris(2-hydroxyethyl)-hexahydrotriazine, 50%;

[0119] Piperazine, 18%;

[0120] Scale inhibitor, 6%;

[0121] Defoamer, 0.10%;

[0122] 2-Amino-2-methyl-1-propanol, 8%;

[0123] Water, remaining amount.

[0124] The purified gas obtained after the above triazine formulation solution absorbs H2S and methanethiol has an H2S content of 1.21 mg / m³. 3 The methanethiol content is 3.27 mg / m³. 3 The sulfur capacity can reach 82.45 g / L, and a large number of bubbles are generated during the absorption process, with no precipitation throughout. When only piperazine is added as a synergist, the sulfur capacity is not significantly improved, and the purification effect of organic sulfur still does not meet the standard.

[0125] Comparative Example 4

[0126] The triazine solvent formulation in this comparative case, calculated by mass percentage, has the following composition:

[0127] 1,3,5-Tris(2-hydroxyethyl)-hexahydrotriazine, 35%;

[0128] Tetrahydrothiophene dioxide, 10%;

[0129] Piperazine, 8%;

[0130] Scale inhibitor, 6%;

[0131] Defoamer, 0.10%;

[0132] 2-Amino-2-methyl-1-propanol, 8%;

[0133] Water, remaining amount.

[0134] The purified gas obtained after the above triazine formulation solution absorbs H2S and methanethiol has an H2S content of 4.54 mg / m³. 3 The methanethiol content is 2.13 mg / m³. 3 The sulfur capacity reached 65.23 g / L, and the solution absorption was stable, but a small amount of precipitation appeared in the latter half of the absorption. The hydrogen sulfide removal rate and sulfur capacity were also unsatisfactory.

[0135] Comparative Example 5

[0136] The triazine solvent formulation in this comparative case, calculated by mass percentage, has the following composition:

[0137] 1,3,5-Tris(2-hydroxyethyl)-hexahydrotriazine, 60%;

[0138] Tetrahydrothiophene dioxide, 10%;

[0139] Piperazine, 8%;

[0140] Scale inhibitor, 6%;

[0141] Defoamer, 0.10%;

[0142] 2-Amino-2-methyl-1-propanol, 8%;

[0143] Water, remaining amount.

[0144] The purified gas obtained after the above triazine formulation solution absorbs H2S and methanethiol has an H2S content of 1.88 mg / m³. 3 The methanethiol content is 1.51 mg / m³. 3 It has a sulfur capacity of up to 98.85 g / L, and the solution absorption is stable with no precipitation during the entire absorption process. However, its sulfur capacity is significantly lower than that of 1,3,5-tris(2-hydroxyethyl)-hexahydrotriazine with a content of 50%, making it less economical.

[0145] Table 1. Results of desulfurization effect test

[0146]

[0147] In summary, when the concentration of 1,3,5-tris(2-hydroxyethyl)-hexahydrotriazine is below 40%, precipitation easily occurs in the solution. When the concentration of 1,3,5-tris(2-hydroxyethyl)-hexahydrotriazine is above 55%, the sulfur capacity begins to decrease significantly. After adding the synergist, the concentration of organic sulfur in the flash steam of the gas field water was controlled and the sulfur capacity was effectively improved. However, a small amount of precipitation still occurs in the solution. After adding an appropriate amount of scale inhibitor and pH stabilizer, the sulfur capacity is greatly improved and no precipitation occurs in the solution throughout the process.

[0148] The method of this invention involves adding a composite additive composed of tetrahydrothiophene dioxide, piperazine, scale inhibitor, defoamer, and 2-amino-2-methyl-1-propanol to a 1,3,5-tris(2-hydroxyethyl)-hexahydrotriazine desulfurization solution. This not only increases the sulfur removal rate, resulting in a triazine desulfurization solution with an H2S removal rate of over 99.9% and a methanethiol removal rate of over 90%, but also solves the problem of precipitation in the triazine solution, increasing its applicability. This formulation exhibits good compatibility with conventional gas field flash steam, but because the solvent in this formulation is a non-renewable solvent, it is more economical and environmentally friendly when used for gas field flash steam with a potential sulfur content of less than 10 kg / d.

[0149] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A triazine formulation solvent for deodorization, characterized in that, Includes the following components: 1,3,5-tris(2-hydroxyethyl)-hexahydrotriazine, synergist, scale inhibitor, defoamer, and pH stabilizer; The synergists include tetrahydrothiophene dioxide and piperazine; The 1,3,5-tris(2-hydroxyethyl)-hexahydrotriazine accounts for 40%~55% of the mass of the formulation solution, the tetrahydrothiophene dioxide accounts for 8%~12% of the mass of the formulation solution, and the piperazine accounts for 6%~10% of the mass of the formulation solution; The scale inhibitor accounts for 6% to 8% of the mass percentage of the formulated solution; The defoamer accounts for 0.1% to 0.2% of the mass of the formulated solution; The pH stabilizer accounts for 6% to 10% of the mass of the formulation solution; The remainder is water.

2. The triazine formulation solvent for deodorization according to claim 1, characterized in that, The tetrahydrothiophene dioxide accounts for 10% of the mass of the formulation solution, and the piperazine accounts for 8% of the mass of the formulation solution.

3. The triazine formulation solvent for deodorization according to claim 1, characterized in that, The 1,3,5-tris(2-hydroxyethyl)-hexahydrotriazine accounts for 50% of the mass of the formulation solution.

4. The application of a triazine formulation solvent for deodorization, characterized in that, Used for gas field water flash steam desulfurization; the deodorizing triazine formulation solvent is the deodorizing triazine formulation solvent according to any one of claims 1 to 3.

5. The application of the triazine formulation solvent for deodorization according to claim 4, characterized in that, The hydrogen sulfide content in the flash steam of the gas field is less than 250 g / m³. 3 Carbon dioxide content less than 500g / m³ 3 Methanethiol content less than 30 mg / m³ 3 The potential sulfur content is less than 10 kg / d.

6. The application of the triazine formulation solvent for deodorization according to claim 5, characterized in that, The hydrogen sulfide content in the flash steam of the gas field is 140 g / m³. 3 -220g / m 3 Carbon dioxide content 350g / m³ 3 -450g / m 3 Methanethiol content 10mg / m 3 -20mg / m 3 .

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