Procaine amine dimer H2S removal agent as well as preparation method and application thereof
By preparing a procainamine dimer H2S remover containing tertiary amine groups and C=N bonds, the problems of pipe blockage and scaling in oil and gas gathering and transportation pipelines were solved, achieving efficient and thorough H2S removal and improving safety.
Patent Information
- Application Number
- CN202410535094.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-04-30
- Publication Date
- 2025-10-31
AI Technical Summary
Existing H2S removal agents are prone to causing pipe blockage in oil and gas gathering and transportation pipelines, and the desulfurization products of traditional triazine desulfurizers are difficult to dissolve, increasing the risk of scaling in on-site pipelines and affecting safety.
The procainamine dimer H2S remover is prepared by aldehyde-amine condensation reaction. It contains tertiary amine groups and C=N bonds, which can quickly absorb H2S and generate soluble or dispersible desulfurization products, avoiding pipe blockage and scaling.
It achieves efficient and thorough H2S removal in oil and gas gathering and transportation pipelines, without the desulfurization products decomposing again, thus improving environmental safety and avoiding pipe blockage and scaling problems.
Smart Images
Figure CN120860784A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of H2S gas removal technology under gas phase and liquid phase environments of natural gas and oil fields. Specifically, it relates to a procainamine dimer H2S removal agent, its preparation method, and its application. Background Technology
[0002] During oil and gas field development, high-temperature heat acts on the oil reservoir, causing the organic sulfides contained in the crude oil to decompose and produce H2S gas; hydrocarbons and organic matter in the crude oil react with sulfates in the reservoir water under high-temperature conditions to produce H2S gas; H2S gas in the sulfate rock layer in the lower formation enters the wellbore; and some workover fluid treatment agents produce H2S gas under high-temperature thermal decomposition and the action of bacteria in the workover fluid.
[0003] When the concentration of H2S exceeds a certain level, it is not only harmful to the human body, but also easily forms a weak acid that causes chemical corrosion, hydrogen embrittlement, and sulfide stress corrosion cracking of metals. Hydrogen embrittlement often leads to the breakage of downhole tubing, explosion of surface manifolds and instruments, damage to wellhead equipment, and even serious blowouts or fires. Therefore, it is necessary to remove H2S.
[0004] Commonly used H2S removal agents, or desulfurizers for short, are numerous and mainly include alkaline hydroxide desulfurizers, metal cation and chelate desulfurizers, oxidizing agent desulfurizers, organic amine desulfurizers, and triazine desulfurizers. Alkaline hydroxide desulfurizers, metal cation and chelate desulfurizers, oxidizing agent desulfurizers, and organic amine desulfurizers can only be used in desulfurization towers and are not effective desulfurizers for oil and gas gathering and transportation pipelines. Triazine desulfurizers can be used for desulfurization of gathering and transportation pipelines with a high desulfurization rate; however, triazine desulfurizers are alkaline organic compounds, and their desulfurization products contain insoluble polysulfides, including 1,3,5-trithiaane, increasing the risk of scaling in on-site pipelines. Pipeline blockage has occurred in several oilfields.
[0005] Therefore, it is necessary to develop a new type of desulfurizing agent that has a strong desulfurization effect, whose desulfurization products are soluble or dispersible, will not cause pipe blockage on site, and is safe and reliable for on-site use. Summary of the Invention
[0006] In view of this, the present invention provides a procainamine dimer H2S removal agent, comprising a procainamine dimer mixture and a stabilizer; wherein the stabilizer is acetamide; preferably, the acetamide accounts for 5-10% of the total mass of the removal agent.
[0007] Further, the procainamine dimer mixture is obtained by aldehyde-amine condensation reaction of procainamine and dialdehyde in a solvent; preferably, the sum of the masses of procainamine and dialdehyde accounts for 30% to 40% of the total mass of the mixture, and the amount of solvent used is 50% to 65% of the total mass of the mixture; preferably, the molar ratio of procainamine to dialdehyde is 2.0 to 2.8:1.
[0008] Furthermore, the dialdehyde substance is preferably a hydrocarbon dialdehyde; the hydrocarbon dialdehyde is preferably glyoxal and / or malondialdehyde.
[0009] Specifically, the principle of the procainamine dimer H2S removal agent is as follows: its chemical structure contains two tertiary amine groups, which can quickly absorb H2S to achieve the purpose of "sulfur fixation"; at the same time, its structure has two C=N bonds, which react with H2S.
[0010] Furthermore, the solvent is one or more of ethanol, isopropanol, and ethylene glycol.
[0011] This invention provides a procainamine dimer H2S removal agent that does not cause scaling problems due to increased system pH. After reacting with H2S, the product is soluble or dispersible, solving the pipe clogging problem caused by the poor solubility of desulfurization products in traditional triazine desulfurizers – this is the biggest innovation of this desulfurizer. The dimer H2S removal agent contains multiple desulfurization groups, including two tertiary amine groups that can rapidly absorb hydrogen sulfide to achieve "sulfur fixation," and two C=N bonds that can react with H2S, resulting in outstanding desulfurization performance. Furthermore, the desulfurization products of this dimer H2S removal agent do not re-decompose and release H2S gas, ensuring thorough desulfurization.
[0012] Another aspect of the present invention provides a method for preparing a procainamine dimer H2S scavenger, comprising the following steps:
[0013] Step 1: Procainamine and dialdehydes undergo an aldehyde-amine condensation reaction in a solvent to obtain a mixture of procainamine dimers.
[0014] Step 2: Add a stabilizer to the procainamine dimer mixture and stir to obtain the procainamine dimer H2S remover.
[0015] Furthermore, in step one, the aldehyde-amine condensation reaction is carried out at 90–120°C for 4–8 hours.
[0016] Furthermore, before adding the stabilizer, the temperature of the procainamine dimer mixture is lowered to 40–50°C.
[0017] Furthermore, after adding the stabilizer, stir for 30–60 minutes.
[0018] The preparation method of this procainamine dimer H2S remover is simple. The obtained procainamine dimer H2S remover will not cause the pH of the system to rise and thus cause scaling problems. The desulfurized products are soluble or dispersible, which solves the problem of pipe blockage caused by the poor solubility of desulfurization products in traditional triazine desulfurizers.
[0019] The third aspect of this invention also proposes an application of a procainamine dimer H2S remover: applying the procainamine dimer H2S remover to the gas phase and liquid phase environments of natural gas and oil fields.
[0020] Furthermore, the ambient temperature of the natural gas and oil field gas phase and liquid phase is 40℃~90℃, and the concentration of hydrogen sulfide is ≤500mg / L.
[0021] The present invention provides an application of a procainamine dimer H2S remover, which is applied to the gas phase and liquid phase environments of natural gas and oil fields containing hydrogen sulfide. It can effectively remove hydrogen sulfide from the environment and improve environmental safety. Attached Figure Description
[0022] Various other advantages and benefits will become apparent to those skilled in the art upon reading the following detailed description of preferred embodiments. The accompanying drawings are for illustrative purposes only and are not intended to limit the invention. Furthermore, the same reference numerals denote the same parts throughout the drawings. In the drawings:
[0023] Figure 1 The preparation process of procainamine dimer provided in the embodiments of the present invention;
[0024] Figure 2 The process diagram provided for the embodiment of the present invention shows the further reaction of salts with H2S;
[0025] Figure 3 Examples of cyclic and chain polysulfide product structures provided in embodiments of the present invention;
[0026] Figure 4 This is a diagram illustrating the aldehyde-amine condensation reaction process of procainamine dimer provided in an embodiment of the present invention.
[0027] Figure 5 Infrared spectrum of the procainamine dimer H2S remover provided in this embodiment of the invention. Detailed Implementation
[0028] The present invention will be described in detail below with reference to specific embodiments and examples, thereby making the advantages and various effects of the present invention more clearly apparent. Those skilled in the art should understand that these specific embodiments and examples are for illustrative purposes only and are not intended to limit the present invention.
[0029] This invention discloses a procainamine dimer H2S removal agent, comprising a procainamine dimer mixture and a stabilizer; the stabilizer is acetamide; preferably, the acetamide accounts for 5-10% of the total mass of the removal agent.
[0030] Further, the procainamine dimer mixture is obtained by aldehyde-amine condensation reaction of procainamine and dialdehyde in a solvent; preferably, the sum of the masses of procainamine and dialdehyde accounts for 30% to 40% of the total mass of the mixture, and the amount of solvent used is 50% to 65% of the total mass of the mixture; preferably, the molar ratio of procainamine to dialdehyde is 2.0 to 2.8:1.
[0031] Furthermore, the dialdehyde substance is preferably a hydrocarbon dialdehyde; the hydrocarbon dialdehyde is preferably glyoxal and / or malondialdehyde.
[0032] Specifically, the principle of the procainamine dimer H2S removal agent is as follows: its chemical structure contains two tertiary amine groups, which can quickly absorb H2S to achieve the purpose of "sulfur fixation"; at the same time, its structure has two C=N bonds, which react with H2S.
[0033] The principle of H2S removal by procainamine dimer H2S removal agent is explained in detail below, taking the product of the aldehyde-amine condensation of glyoxal and procainamine as an example:
[0034] Step 1: The two tertiary amine groups react with H2S to form a salt, as shown in the diagram below (attached). Figure 1 As shown in the figure;
[0035]
[0036] Step 2: Salts further react with H2S, as shown in the diagram below (attached). Figure 2 As shown in the figure;
[0037]
[0038] Step 3: The hemiacetal in the product is unstable and can undergo various polymerization and condensation reactions to produce various cyclic and chain polysulfide products, as shown in the figure below (attached). Figure 3 As shown in the figure;
[0039]
[0040] These substances contain aldehyde groups, and when the temperature is high or the H2S concentration is high, they will continue to undergo desulfurization reactions, which will further enhance the desulfurization effect.
[0041] Furthermore, the solvent is one or more of ethanol, isopropanol, and ethylene glycol.
[0042] This invention provides a procainamine dimer H2S removal agent that does not cause scaling problems due to increased system pH. After reacting with H2S, the product is soluble or dispersible, solving the pipe clogging problem caused by the poor solubility of desulfurization products in traditional triazine desulfurizers – this is the biggest innovation of this desulfurizer. The dimer H2S removal agent contains multiple desulfurization groups, including two tertiary amine groups that can rapidly absorb hydrogen sulfide to achieve "sulfur fixation," and two C=N bonds that can react with H2S, resulting in outstanding desulfurization performance. Furthermore, the desulfurization products of this dimer H2S removal agent do not re-decompose and release H2S gas, ensuring thorough desulfurization.
[0043] This invention further discloses a method for preparing a procainamine dimer H2S removal agent, taking glyoxal as an example, including the following steps:
[0044] (1) Procainamine and glyoxal are subjected to an aldehyde-amine condensation reaction in a solvent at 90–120°C for 4–8 hours to obtain a mixture of procainamine dimers. The aldehyde-amine condensation reaction process of the procainamine dimer is described in reference [reference needed]. Figure 4 As shown;
[0045] (2) Cool down to 40-50℃, add stabilizer, stir for 30-60 min, and the synthesis reaction is completed to obtain procainamine dimer H2S remover.
[0046] Figure 5 This is the infrared spectrum of the procainamine dimer H2S remover prepared in this embodiment. Based on this, it can be determined that the product contains procainamine dimer. In the figure, at 1560 cm⁻¹... -1 The characteristic absorption peak at C=N of the imine is observed (reference). That is, -C = N - AR. Characteristic peak ≈ 1555 cm⁻¹ -1 The presence of this peak indicates that the target product, procainamine dimer, has been synthesized; 1641 cm⁻¹ -1 The absorption peak at 3396 cm⁻¹ represents the C=O bond absorption peak of the intramolecular amide. -1 1039cm -1 and 1097cm -1 The peaks at points 1 and 2 represent the -OH stretching vibration and -CO- stretching vibration of the solvent alcohol in the desulfurizing agent, respectively.
[0047] The preparation method of this procainamine dimer H2S remover is simple. The obtained procainamine dimer H2S remover will not cause the pH of the system to rise and thus cause scaling problems. The desulfurized products are soluble or dispersible, which solves the problem of pipe blockage caused by the poor solubility of desulfurization products in traditional triazine desulfurizers.
[0048] This invention also discloses an application of a procainamine dimer H2S remover: the procainamine dimer H2S remover is applied to the gas and liquid phases of natural gas and oil fields. Further, the temperature of the natural gas and oil field gas and liquid phase environments is 40℃~90℃, and the concentration of hydrogen sulfide is ≤500mg / L.
[0049] The following will provide a detailed description of the procainamine dimer H2S remover, its preparation method, and its application, using specific embodiments and experimental data, with glyoxal as an example.
[0050] Example 1
[0051] This embodiment provides a procainamine dimer H2S removal agent and its preparation method as follows:
[0052] 1) Procainamine and glyoxal (molar ratio 2.0:1, mass fraction 40%) were subjected to an aldehyde-amine condensation reaction in a solvent (ethanol with a mass fraction of 50%) at 90°C for 8 hours to obtain a mixed solution of procainamine dimer.
[0053] 2) Cool down to 40℃, add stabilizer (acetamide with a mass fraction of 10%), stir for 60 min, and the synthesis reaction is completed to obtain procainamine dimer H2S remover.
[0054] Example 2
[0055] This embodiment provides a procainamine dimer H2S removal agent and its preparation method as follows:
[0056] 1) Procainamine and glyoxal (molar ratio 2.5:1, mass fraction 35%) were subjected to aldehyde-amine condensation reaction in a solvent (ethanol with a mass fraction of 57%) at 90°C for 6 hours to obtain a mixed solution of procainamine dimer.
[0057] 2) Cool down to 40℃, add stabilizer (acetamide with a mass fraction of 8%), stir for 60 min, and the synthesis reaction is completed to obtain procainamine dimer H2S remover.
[0058] Example 3
[0059] This embodiment provides a procainamine dimer H2S removal agent and its preparation method as follows:
[0060] 1) Procainamine and glyoxal (molar ratio 2.8:1, mass fraction 30%) were subjected to an aldehyde-amine condensation reaction in a solvent (ethanol with a mass fraction of 65%) at 90°C for 6 hours to obtain a mixed solution of procainamine dimer.
[0061] 2) Cool down to 40℃, add stabilizer (acetamide with a mass fraction of 5%), stir for 60 min, and the synthesis reaction is completed to obtain procainamine dimer H2S remover.
[0062] Comparative Example 1
[0063] A triazine H2S removal agent is prepared as follows:
[0064] Ethanolamine and formaldehyde were subjected to an amine-aldehyde condensation reaction at 1:1 molar ratio at 100℃ for 6 h to synthesize 1,3,5-tris(2-hydroxyethyl)-hexahydrotriazine, which is a common triazine H2S remover.
[0065] Comparative Example 2
[0066] A procainamine dimer H2S removal agent and its preparation are as follows:
[0067] Procainamine and glyoxal (molar ratio 2.8:1, mass fraction 35%) were subjected to an aldehyde-amine condensation reaction in a solvent (65% mass fraction ethanol) at 90°C for 6 hours to obtain a procainamine dimer mixture H2S removal agent.
[0068] The present invention provides an application of a procainamine dimer H2S remover, which is applied to the gas phase and liquid phase environments of natural gas and oil fields containing hydrogen sulfide. It can effectively remove hydrogen sulfide from the environment and improve environmental safety.
[0069] The effectiveness of the H2S removal agents obtained in the above embodiments and comparisons was evaluated:
[0070] In a sealed container containing 1L of solution, environments simulating different concentrations of hydrogen sulfide and an equal concentration of H2S removal agent were established. The mixture was stirred for 1 hour at a specific temperature. The hydrogen sulfide concentration was then determined using GB / T 11060.1-2023 "Determination of Sulfur Compounds in Natural Gas - Part 1: Determination of Hydrogen Sulfide Content by Iodometric Method". The desulfurization rate was calculated, and the presence of precipitates in the solution was observed. Specific test results are shown in Table 1.
[0071] Table 1. Product Performance Test Results of Implementation Cases
[0072]
[0073]
[0074] As shown in Table 1, the procainamine dimer H2S remover exhibits excellent desulfurization performance in gaseous and liquid environments with temperatures ranging from 40℃ to 90℃ and hydrogen sulfide concentrations ≤500mg / L. Furthermore, adding an equal amount of procainamine dimer H2S remover with hydrogen sulfide results in a desulfurization rate >85%. The desulfurization reaction products are stable and do not re-decompose and release H2S gas. Desulfurization is thorough, and the desulfurization products are water-soluble, preventing pipeline blockage.
[0075] In summary, the procainamine dimer H2S remover provided in this embodiment does not cause scaling problems due to increased system pH. After reacting with H2S, the product of this procainamine dimer H2S remover is soluble or dispersible, solving the pipe clogging problem caused by the poor solubility of desulfurization products in traditional triazine desulfurizers, which is the biggest innovation of this desulfurizer. The dimer H2S remover molecule contains multiple desulfurization groups, including two tertiary amine groups that can quickly absorb hydrogen sulfide to achieve "sulfur fixation," and two C=N bonds that can react with H2S, resulting in outstanding desulfurization effect. Furthermore, the desulfurization products of this dimer H2S remover do not decompose and release H2S gas again, ensuring thorough desulfurization.
[0076] It should be noted that in the description of this invention, the terms "upper", "lower", "left", "right", "inner", "outer", etc., which indicate directions or positional relationships, are based on the directions or positional relationships shown in the accompanying drawings. This is only for the convenience of description and is not intended to indicate or imply that the device or element must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, it should not be construed as a limitation of this invention.
[0077] Furthermore, it should be noted that, in the description of this invention, unless otherwise explicitly specified and limited, the terms "installation," "connection," and "joining" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components. Those skilled in the art can understand the specific meaning of the above terms in this invention according to the specific circumstances.
[0078] Obviously, those skilled in the art can make various modifications and variations to this invention without departing from its spirit and scope. Therefore, if these modifications and variations fall within the scope of the claims of this invention and their equivalents, this invention also intends to include these modifications and variations.
Claims
1. A procainamine dimer H2S removal agent, characterized in that, It includes a mixture of procainamine dimers and a stabilizer; the stabilizer is acetamide; preferably, the acetamide accounts for 5-10% of the total mass of the remover.
2. The procainamine dimer H2S remover according to claim 1, characterized in that, The procainamine dimer mixture is obtained by condensation reaction of procainamine and dialdehyde in a solvent via an aldehyde-amine condensation reaction; preferably, the sum of the masses of the procainamine and the dialdehyde accounts for 30% to 40% of the total mass of the mixture, and the amount of solvent used is 50% to 65% of the total mass of the mixture; preferably, the molar ratio of the procainamine to the dialdehyde is 2.0 to 2.8:
1.
3. The procainamine dimer H2S remover according to claim 1, characterized in that, The dialdehyde substance is preferably a hydrocarbon dialdehyde; the hydrocarbon dialdehyde is preferably glyoxal and / or malondialdehyde.
4. The procainamine dimer H2S remover according to claim 2, characterized in that, The solvent is one or more of ethanol, isopropanol, and ethylene glycol.
5. A method for preparing a procainamine dimer H2S scavenger, characterized in that, Includes the following steps: Step 1: Procainamine and dialdehydes undergo an aldehyde-amine condensation reaction in a solvent to obtain procainamine. Lucainamine dimer mixture; Step 2: Add a stabilizer to the procainamine dimer mixture and stir to obtain procain. Amine dimer H2S removal agent.
6. The method for preparing the procainamine dimer H2S remover according to claim 5, characterized in that, In step one, the aldehyde-amine condensation reaction is carried out at 90–120°C for 4–8 hours.
7. The method for preparing the procainamine dimer H2S remover according to claim 5, characterized in that, Before adding the stabilizer, the temperature of the procainamine dimer mixture should be lowered to 40–50°C.
8. The method for preparing the procainamine dimer H2S remover according to claim 5, characterized in that, After adding the stabilizer, stir for 30–60 minutes.
9. The application of a procainamine dimer H2S removal agent, characterized in that, The procainamine dimer H2S remover is applied to the gas and liquid phases of natural gas and oil fields.
10. The application of the procainamine dimer H2S remover according to claim 9, characterized in that, The ambient temperature of the natural gas and oilfield gas and liquid phases is 40℃~90℃, and the concentration of hydrogen sulfide is ≤500mg / L.