A sulfur particle anti-agglomerating agent for high-sulfur gas fields and a preparation method thereof

Abstract

The present application relates to the oil field chemistry and surfactant technical field, especially a kind of for high sulfur gas field sulfur particle anti-agglomerant and preparation method.The elemental sulfur anti-agglomerant provided in the present application includes the following mass fraction components: potassium stearate 2~5 parts, sodium lignosulfonate 3~9 parts, sodium p-toluenesulfonate 4~8 parts, inorganic salt adjuvant 11~23 parts and solvent 60~75 parts.The process flow of the elemental sulfur anti-agglomerant prepared in the present application is simple, and the economic cost is low, by adjusting the synergism and compatibility between surfactants, improve its dispersed sulfur particle performance, applicable to sulfur deposition prevention and control means in high sulfur gas field.

Description

Technical Field

[0001] This invention relates to the field of oilfield chemistry and surfactant technology, and in particular to an anti-agglomeration agent for sulfur particles in high-sulfur gas fields and its preparation method. Background Technology

[0002] With the changing global energy structure, natural gas has emerged as a clean and efficient energy source, occupying an important position in the global energy mix. Therefore, developing more challenging gas fields has become a necessary measure to solve the natural gas energy supply problem, with high-sulfur gas fields attracting widespread attention. In high-sulfur natural gas reservoirs, sulfur typically exists as a mixture of sulfur, hydrogen sulfide, and persulfide. During reservoir development and storage, changes in temperature and pressure cause sulfur particles in the gas phase to precipitate, grow, and aggregate, blocking gas flow channels and affecting stable production and operational safety during well and storage processes. Therefore, exploring effective sulfur deposition control measures is crucial.

[0003] Currently, the main technologies for controlling sulfur deposition in high-sulfur gas fields include: sulfur deposition prediction technology, production process optimization technology, physical control technology, and chemical control technology. Sulfur deposition prediction primarily involves analyzing critical sulfur solubility through experiments, predictive models, and molecular simulations. Studies show that sulfur solubility in the gas phase increases with increasing pressure and temperature. Production process optimization technology mainly improves processes by controlling pressure, temperature, or gas extraction rate. However, after natural gas passes through throttling devices, sulfur particles easily precipitate and form sulfur deposits as pressure and temperature decrease, clogging pipelines and equipment. Physical control technology mainly involves cleaning pipelines to remove sulfur deposits, but cleaning is a post-event treatment and cannot alleviate sulfur deposition. Chemical control technology mainly involves injecting sulfur-dissolving agents into the pipeline, which is simple and quick to treat sulfur deposits. However, common sulfur-dissolving agents such as dimethyl disulfide (DMDS) and N,N-dimethylformamide (DMF) are highly toxic and pose a threat to human health. In summary, while there are various methods for controlling sulfur deposition, they are mainly post-event treatments and cannot effectively control the formation of sulfur deposits.

[0004] Surfactants, due to their emulsifying, foaming, wetting, surface-active, and phase-separating properties, are widely used in various industrial production processes, with their dispersion effect on solid particles being particularly prominent. In the preparation of nanomaterials, surfactants can effectively inhibit the aggregation and growth of nanoparticles. The interaction between the hydrophobic groups of sodium dodecyl sulfate (SDS) and the surface of carbon nanotubes can enhance the hydrophilicity of carbon nanotubes, effectively preventing their aggregation in solvents. In water-based coatings, sodium dodecylbenzene sulfonate (SDBS) is commonly used to disperse titanium dioxide (TiO2). SDBS adsorbs onto the TiO2 surface, generating electrostatic repulsion between particles. Furthermore, due to steric hindrance, when TiO2 particles adsorbed with SDBS approach each other, the adsorption layer is compressed, further hindering particle aggregation.

[0005] In summary, few studies currently utilize surfactants as anti-agglomeration agents to control sulfur deposition in high-sulfur gas fields. Therefore, developing a surfactant that can be added to high-sulfur gas fields to mitigate sulfur deposition is a pressing technical problem that needs to be solved in this field. Summary of the Invention

[0006] The purpose of this invention is to provide an anti-agglomeration agent for sulfur particles in high-sulfur gas fields and a preparation method thereof, so as to reduce the average particle size of sulfur particles, improve dispersibility, and thus effectively slow down sulfur deposition.

[0007] To achieve the above-mentioned objectives, the present invention provides the following technical solution: One of the technical solutions of the present invention is a single-element sulfur anti-polymerization agent, comprising the following components in parts by weight: 2-5 parts potassium stearate, 3-9 parts sodium lignosulfonate, 4-8 parts sodium p-toluenesulfonate, 11-23 parts inorganic salt additives, and 60-75 parts solvent.

[0008] The second technical solution of this invention is a method for preparing a single-element sulfur anti-polymerization agent, comprising the following steps: Potassium stearate, sodium lignosulfonate, sodium p-toluenesulfonate, inorganic salt additives, and solvents are mixed to obtain a single-element sulfur anti-polymerization agent.

[0009] The third technical solution of the present invention is the application of the above-mentioned elemental sulfur anti-polymerization agent in the development of high-sulfur gas fields.

[0010] Compared with the prior art, the present invention has the following beneficial effects: Compared to traditional sulfur solvents, the elemental sulfur anti-agglomeration agent of this invention utilizes surfactants for adsorption and dispersion. Adsorbed on the surface of solid particles, it effectively prevents particle aggregation and promotes particle dispersion under the influence of electrostatic repulsion, van der Waals forces, and steric hindrance. By using a compound surfactant as the main component of the sulfur deposition mitigation agent, it exhibits lower toxicity and biodegradability compared to traditional sulfur solvents, making it more environmentally friendly. This method of inhibiting sulfur particle aggregation and mitigating sulfur deposition in pipelines provides a new approach to sulfur deposition control in high-sulfur gas fields.

[0011] The present invention provides a simple and cost-effective process for preparing elemental sulfur anti-agglomeration agents. Compared with traditional process optimization and post-treatment methods, by adjusting the synergy and compatibility between surfactants and adding them to high-sulfur gas fields, the agent improves the performance of dispersing sulfur particles and inhibits the aggregation and growth of sulfur particles from the source. It is suitable for sulfur deposition control in high-sulfur gas fields. Detailed Implementation

[0012] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0013] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0014] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0015] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be obvious to those skilled in the art. This application specification and embodiments are merely exemplary.

[0016] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0017] All raw materials used in this invention can be obtained commercially or prepared using existing technologies.

[0018] This invention provides a single-element sulfur anti-polymerization agent, comprising the following components in parts by weight: 2-5 parts potassium stearate, 3-9 parts sodium lignosulfonate, 4-8 parts sodium p-toluenesulfonate, 11-23 parts inorganic salt additives, and 60-75 parts solvent.

[0019] In this invention, the elemental sulfur anti-polymerization agent includes 2 to 5 parts of potassium stearate, for example, 2 parts, 3 parts, 4 parts or 5 parts.

[0020] In this invention, the elemental sulfur anti-polymerization agent includes 3 to 9 parts of sodium lignosulfonate, for example, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts or 9 parts.

[0021] In this invention, the elemental sulfur anti-polymerization agent includes 4 to 8 parts of sodium p-toluenesulfonate, for example, 4 parts, 5 parts, 6 parts, 7 parts or 8 parts.

[0022] In this invention, the elemental sulfur anti-polymerization agent includes 11 to 23 parts of inorganic salt additive, for example, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22 or 23 parts.

[0023] In this invention, the elemental sulfur anti-polymerization agent comprises 60 to 75 parts of solvent, for example, 60 parts, 64 parts, 69 parts, 74 parts or 75 parts.

[0024] In this invention, the inorganic salt additive is a mixture of potassium sulfate solution and potassium chloride solution.

[0025] In this invention, the solvent is water.

[0026] In this invention, the mass fraction of the potassium sulfate solution is 1-5%, for example, it can be 1%, 2%, 3%, 4% or 5%; the mass fraction of the potassium chloride solution is 1-5%, for example, it can be 1%, 2%, 3%, 4% or 5%.

[0027] In this invention, the mass ratio of potassium sulfate solution to potassium chloride solution is 5~9:6~14.

[0028] This invention also provides a method for preparing the above-mentioned elemental sulfur anti-polymerization agent, comprising the following steps: Potassium stearate, sodium lignosulfonate, sodium p-toluenesulfonate, inorganic salt additives, and solvents are mixed to obtain a single-element sulfur anti-polymerization agent.

[0029] In this invention, the mixing speed is 100~200 rpm, for example, 120 rpm, 150 rpm, 180 rpm or 200 rpm, the mixing time is 5~10 min, for example, 5 min, 6 min, 8 min or 10 min, and the temperature is 25~40℃, for example, 25℃, 30℃, 35℃ or 40℃.

[0030] In the implementation of this invention, the preparation method of the elemental sulfur anti-polymerization agent can also be as follows: (1) First, dissolve potassium stearate in part of the solvent, use an ultrasonic dispersion device to mix it thoroughly, and then heat it to 25~40℃ to obtain the first surfactant solution and keep it warm for later use; (2) Dissolve sodium lignosulfonate and sodium p-toluenesulfonate in another part of the solvent, mix them thoroughly using an ultrasonic dispersion device, heat to 25~40℃, slowly add the sodium lignosulfonate solution to the sodium p-toluenesulfonate solution, and stir at a stirring speed of 100~150rpm. Finally, maintain the temperature at 25~40℃ to obtain the second surfactant solution for later use. (3) Mix K2SO4 solution and KCl solution thoroughly and keep at 25~40℃ to obtain inorganic salt auxiliary solution for later use; (4) The first surfactant solution, the second surfactant solution and the inorganic salt additive solution are stirred at 25~40℃ at a stirring speed of 150~200rpm for 5~10min to obtain the elemental sulfur anti-polymerization agent.

[0031] The present invention also provides the application of the above-mentioned elemental sulfur anti-polymerization agent in the development of high sulfur gas fields.

[0032] In practical applications, elemental sulfur anti-polymerization agent is continuously or intermittently injected into the gas system to be treated at a concentration of 1-5% v / v, so that the anti-polymerization agent stays in the pipeline for at least 30 minutes, in order to reduce the average particle size of sulfur particles and prevent deposition.

[0033] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0034] In the embodiments of the present invention, the mass fraction of K2SO4 solution is 1% and the mass fraction of KCl solution is 1%.

[0035] Example 1 A single-element sulfur anti-polymerization agent, by weight, comprises 2 parts potassium stearate, 3 parts lignin sulfonic acid, 4 parts sodium p-toluenesulfonate, 6 parts K2SO4 solution, 10 parts KCl solution, and 75 parts water.

[0036] Preparation method of elemental sulfur anti-polymerization agent: According to the above mass proportions, potassium stearate, lignin sulfonic acid, sodium p-toluenesulfonate, K2SO4 solution, and KCl solution were added to water and stirred at a stirring speed of 200 rpm for 10 min, while maintaining the temperature at 40℃, to obtain elemental sulfur anti-polymerization agent.

[0037] Example 2 A single-element sulfur anti-polymerization agent, by weight, comprises 3 parts potassium stearate, 4 parts lignin sulfonic acid, 5 parts sodium p-toluenesulfonate, 7 parts K2SO4 solution, 7 parts KCl solution, and 74 parts water.

[0038] The preparation method of the elemental sulfur anti-polymerization agent is the same as in Example 1.

[0039] Example 3 A single-element sulfur anti-polymerization agent, by weight, comprises 4 parts potassium stearate, 5 parts lignin sulfonic acid, 6 parts sodium p-toluenesulfonate, 8 parts K2SO4 solution, 8 parts KCl solution, and 69 parts water.

[0040] The preparation method of the elemental sulfur anti-polymerization agent is the same as in Example 1.

[0041] Example 4 A single-element sulfur anti-polymerization agent, by weight, comprises 5 parts potassium stearate, 6 parts lignin sulfonic acid, 7 parts sodium p-toluenesulfonate, 9 parts K2SO4 solution, 9 parts KCl solution, and 64 parts water.

[0042] The preparation method of the elemental sulfur anti-polymerization agent is the same as in Example 1.

[0043] Comparative Example 1 The only difference from Example 1 is that potassium stearate is omitted.

[0044] Comparative Example 2 The only difference from Example 1 is that sodium lignosulfonate and sodium p-toluenesulfonate are omitted.

[0045] Comparative Example 3 The only difference from Example 1 is that the K2SO4 solution and KCl solution are omitted.

[0046] Test Example 1 The performance of the elemental sulfur particle anti-agglomeration agents in Examples 1-4 and Comparative Examples 1-3 was tested using the contact angle measurement method. The contact angle measurement clearly shows the wetting effect of the surfactant on the sulfur powder at different mass fractions. A smaller contact angle indicates better wetting of the sulfur powder by the elemental sulfur particle anti-agglomeration agent.

[0047] The wettability of sulfur powder to a blank group of distilled water and the wettability of the elemental sulfur particle anti-agglomeration agents in Examples 1-4 and Comparative Examples 1-3 to sulfur powder were measured using the seated drop method. Dried sulfur powder was sieved, selecting powder with a particle size between 80 and 100 mesh. The selected sample sulfur powder was pressed to 15 MPa using an FW-4A-1 powder press and held for 3 minutes to produce uniformly thick sheets. The contact angle of the elemental sulfur particle anti-agglomeration agent was measured using a contact angle meter. The measurement method used was the seated drop method. The liquid state of the solution dropped onto the sulfur powder sheet was photographed, and the photographed state of the droplet on the sulfur powder sheet was projected onto a computer screen. The computer automatically fitted the angle between the droplet and the gas-solid interface, and the measured data was the contact angle. The measurement was repeated three times, and the average value was taken.

[0048] Table 1. Test results of wetting performance of elemental sulfur particle anti-agglomeration agent

[0049] The contact angle between distilled water and sulfur powder tablets was measured to be 77.2° through experiments.

[0050] Comparing the experimental results of Examples 1-4, it can be seen that the elemental sulfur particle anti-agglomeration agent has better wettability of sulfur powder compared to distilled water.

[0051] Compared with Examples 1-4, as the concentration increases, the contact angle decreases, and the wettability of the anti-polymerization agent on the sulfur powder gradually increases.

[0052] Test Example 2 This invention measures the mass of sulfur particles of different sizes by measuring the mass of sulfur powder in standard sieves of different mesh sizes, and tests the dispersion performance of elemental sulfur particle anti-agglomeration agents.

[0053] The experimental steps are as follows: 1) Cleaning standard sieves: Clean standard sieves of different mesh sizes and then dry them in a high-temperature drying oven; 2) Initial mass weighing of standard sieves: Place the dried standard sieves on an electronic balance and weigh them one by one. Repeat the weighing three times, take the average value, and record the initial mass of the standard sieves of different mesh sizes and the standard sieves on the bottom plate. 3) Weigh the sulfur powder: Pour the sulfur powder into standard sieves with a mesh size of 80 mesh and 100 mesh for screening, and weigh about 10g of sulfur powder with a particle size range of 150μm~200μm. 4) Stirring and drying: Pour the weighed sulfur powder into the prepared elemental sulfur granule anti-agglomeration agent and stir with a mechanical stirrer for 20 seconds. Pour the elemental sulfur granule anti-agglomeration agent and sulfur powder together into a standard sieve whose initial mass has been recorded, and then place it in a high-temperature drying oven to dry. 5) Weighing the final mass of the standard sieves: After the sulfur powder is dried, it is thoroughly shaken. After shaking and sieving, the masses of the standard sieves and the base plate of different mesh sizes are weighed in sequence. Then, the initial mass of the standard sieves is subtracted to obtain the mass of sulfur powder in the standard sieves of different mesh sizes.

[0054] 6) Repeat the experiment three times and take the average value.

[0055] Add 10g of sulfur powder with a particle size range of 80 to 100 mesh to the distilled water blank group, Examples 1-4, and Comparative Examples 1-3. Stir with a mechanical stirrer for about 15-20 seconds, then pour into a standard sieve. Place the standard sieve in a high-temperature drying oven at 60°C for 8 hours until the sulfur powder is completely dried, then shake. After the sieving operation is completed, weigh the standard sieves of different mesh sizes sequentially and record the mass of sulfur powder in the standard sieves of different mesh sizes.

[0056] The mass of sulfur powder is calculated using the following formula.

[0057] Where: — Initial mass of standard sieves with different mesh sizes; —Total mass of the standard sieve containing sulfur powder; —The quality of sulfur powder in standard sieves with different mesh sizes.

[0058] This method uses a weighted average calculation based on equidistant segmentation to determine the average particle size of sulfur particles. The median value of each particle size range is used as the representative particle size, multiplied by its respective proportion, and the average particle size is determined by summing these values. After sieving, the mass of sulfur powder with a particle size >150 μm is assumed to be... The mass of sulfur powder with a particle size of 125μm~150μm is The mass of sulfur powder with a particle size of 100μm~125μm is The mass of sulfur powder with a particle size of 90μm~100μm is The mass of sulfur powder with a particle size of 75μm~90μm is The mass of sulfur powder <75μm is The total mass of the dried sulfur powder is The mass fraction of sulfur particles in each particle size range is calculated as follows: Where: — mass fraction of sulfur powder in different particle size ranges; —The quality of sulfur powder in different particle size ranges.

[0059] The average sulfur particle size is calculated using the following formula: In the formula: —The average particle size of the sulfur particles; —For particle size > 150 μm, take 162.5 μm; —The particle size is between 125μm and 150μm, and we take 137.5μm; —The particle size is between 100μm and 125μm, and we take 112.5μm; —The particle size is between 90μm and 100μm, and we take 95μm; —The particle size is between 75μm and 90μm, and we take 82.5μm; —If the particle size is <75μm, take 62.5μm.

[0060] The initial mass of standard sieves with different mesh sizes is shown in Table 2 below.

[0061] Table 2. Test results of dispersibility of elemental sulfur particle anti-agglomeration agent

[0062] Comparing Examples 1-4, the elemental sulfur particle anti-agglomeration agent in Example 3 exhibited the best dispersibility, with an average sulfur particle size of 91.6100 μm. In contrast, the average particle size of sulfur particles dispersed in distilled water was 115.6754 μm, while the average particle size of sulfur particles dispersed in comparative example one was 102.7484 μm; the average particle size of sulfur particles dispersed in comparative example two was 103.2597 μm; and the average particle size of sulfur particles dispersed in comparative example three was 100.402 μm. Compared to deionized water and the comparative examples, the elemental sulfur particle anti-agglomeration agent in Example 3 demonstrated superior effectiveness. The surfactant complex system increases the negative charge density on the sulfur particle surface, further enhancing electrostatic repulsion and more effectively preventing sulfur particle aggregation. The thickness and complexity of the adsorption layer formed on the sulfur particle surface by the surfactant complex system also increase. When sulfur particles adsorbed with surfactant molecules approach each other, the steric hindrance effect generated by the mutual compression of molecules in the adsorption layer becomes more significant, more effectively resisting collisions and proximity between sulfur particles, further enhancing the dispersion of sulfur powder.

[0063] Comparing Examples 1-4 and Comparative Examples 1-3, the component ratio of the elemental sulfur particle anti-agglomeration agent in Example 3 is the optimal ratio.

[0064] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A single-element sulfur anti-polymerization agent, characterized in that, It includes the following components in parts by weight: 2-5 parts potassium stearate, 3-9 parts sodium lignosulfonate, 4-8 parts sodium p-toluenesulfonate, 11-23 parts inorganic salt additives, and 60-75 parts solvent.

2. The elemental sulfur anti-polymerization agent according to claim 1, characterized in that, The inorganic salt additive is a mixture of potassium sulfate solution and potassium chloride solution.

3. The elemental sulfur anti-polymerization agent according to claim 1, characterized in that, The solvent is water.

4. The elemental sulfur anti-polymerization agent according to claim 2, characterized in that, The potassium sulfate solution has a mass fraction of 1-5%; the potassium chloride solution has a mass fraction of 1-5%.

5. The elemental sulfur anti-polymerization agent according to claim 1, characterized in that, The mass ratio of potassium sulfate solution to potassium chloride solution is 5~9:6~14.

6. The method for preparing the elemental sulfur anti-polymerization agent according to any one of claims 1 to 5, characterized in that, Includes the following steps: Potassium stearate, sodium lignosulfonate, sodium p-toluenesulfonate, inorganic salt additives, and solvents are mixed to obtain a single-element sulfur anti-polymerization agent.

7. The preparation method according to claim 6, characterized in that, The mixing speed is 100~200 rpm, the time is 5~10 min, and the temperature is 25~40℃.

8. The application of the elemental sulfur anti-polymerization agent according to any one of claims 1 to 5 in the development of high-sulfur gas fields.

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