Solid sulfur removal agent as well as preparation method and application thereof

Abstract

The invention relates to a solid sulfur removal agent as well as a preparation method and application thereof. Soluble metal salt, dimethylimidazole and an amino modifier react in an organic solvent, and solid-liquid separation is performed; the soluble metal salt is soluble zinc metal salt or soluble cobalt metal salt; the amino modifier is one of ammonium dodecyl sulfate, tetradecylamine, hexadecylamine, octadecylamine, 9-octadecene amine, and 3-triethoxysilyl-1-propylamine; and the catalyst is a catalyst. The mass ratio of the soluble metal salt to the dimethylimidazole to the amino modifier is (2-4): (4-10): (0.2-0.9). The prepared metal organic framework material is used as a solid sulfur removal agent, has a good sulfur removal effect in the drilling fluid, can reduce the filter loss of the drilling fluid and improve the rheological property of the drilling fluid, can be used in water-based and oil-based drilling fluids, and meets the requirements of on-site drilling sulfur removal construction.

Description

Technical Field

[0001] The invention relates to a solid desulfurizer, a preparation method and application thereof, and belongs to the technical field of oil drilling fluid. Background Art

[0002] Hydrogen sulfide (H2S) is a highly toxic, flammable, explosive, colorless, weakly acidic gas with a rotten egg smell. It is heavier than air (density 1.176 g / cm 3 ) is soluble in water and oil, with a solubility of approximately 3000 mg / L in water at room temperature and pressure, and its solubility decreases with increasing temperature. H2S is 5-6 times more toxic than CO. Exposure to a concentration of 10 ppm can cause eye irritation; at 100 ppm, coughing, eye irritation, and loss of smell can occur within 3-15 minutes; at 1000 ppm, unconsciousness can occur immediately, resulting in permanent brain damage or brain death. Furthermore, H2S mixtures with air at concentrations of 4.3% to 4.5% can explode.

[0003] As oil production continues, many problems still exist in the actual process of production. For example, the Sichuan Basin, Tarim Basin, and Ordos Basin in my country all contain high-sulfur gas reservoirs. During the drilling process of high-sulfur gas reservoirs, hydrogen sulfide intrusion into the drilling fluid will cause the following hazards: (1) Pollution of the drilling fluid. The entry of hydrogen sulfide gas into the drilling fluid system will have an adverse effect on the comprehensive properties of the drilling fluid, causing a decrease in the specific gravity of the drilling fluid, deterioration of the rheological properties, and a decrease in the pH value, which seriously affects the efficiency of drilling construction; (2) Corrosion of metal materials and rubber materials such as drilling pipes, oil layer casings, and ground blowout prevention facilities. In addition, when drilling in high-sulfur formations, the presence of hydrogen sulfide may cause serious electrochemical corrosion and hydrogen embrittlement fracture hazards to downhole pipes and drilling equipment. In particular, after the drill bit produces hydrogen embrittlement, it may cause it to suddenly break, which is easy to cause serious safety accidents; (3) Inhalation of a small amount of hydrogen sulfide gas can cause organ poisoning in humans, and in severe cases, it can cause death, which is extremely harmful to the health of on-site construction workers. Therefore, it is necessary to remove all or most of the hydrogen sulfide underground or during the production process to eliminate or reduce accidents and hazards caused by hydrogen sulfide.

[0004] Currently, desulfurization agents are mainly added to drilling fluids to improve the removal efficiency of H2S in water-based or oil-based drilling fluids through physical adsorption or chemical reaction. Commonly used desulfurization agents include two types: liquid desulfurization agents and solid desulfurization agents.

[0005] Liquid desulfurizers mainly include triazines, alcohol amines, etc., which mainly remove sulfur through chemical reactions and have high sulfur removal efficiency, but have disadvantages such as foaming, product instability, and poor temperature resistance. The Chinese invention patent application publication number CN116640561A discloses a high-temperature resistant multifunctional liquid desulfurizer for drilling fluid and a preparation method thereof. Specifically, the liquid desulfurizer includes the following raw material ratios, calculated by weight: main agent 1: 1,3,5-tributyl-hexahydro-s-triazine, 30-40%; main agent 2: triethanolamine, 10-15%; main agent 3: nano zinc oxide, 10-15%; solvent: cyclopentane, 5-10%; adsorbent: graphene oxide, 10-15%; suspending agent: carboxymethyl cellulose, 0.1-0.2%; defoaming agent: one or more of methyl silicone oil, ethyl silicone oil, phenyl silicone oil, and methylphenyl silicone oil, 0.1-0.5%; dispersant: one or two of sodium polyacrylate and sodium polycarboxylate, 1-5%; and the rest is water. This desulfurizer, based on the high-efficiency desulfurization of triazine and alcoholamine liquid desulfurizers, incorporates graphene oxide and nano-zinc oxide to enhance its adsorption capacity and temperature resistance, meeting the needs of on-site drilling desulfurization operations. However, its complex formulation and high cost hinder its widespread application.

[0006] Solid desulfurizers include copper-based desulfurizers, iron-based desulfurizers and zinc-based desulfurizers. Among them, basic zinc carbonate is widely used due to its relatively high desulfurization efficiency. Basic zinc carbonate is an amphoteric substance. It has good solubility when the pH is greater than 11, but it is easy to cause solid phase aggregation and flocculation. When the pH is 9-11, the solubility is not high and most of it is granular, resulting in poor desulfurization effect. The performance reaches its best when the pH is less than 9. The pH value limits its effectiveness during use. Summary of the Invention

[0007] The first object of the present invention is to provide a method for preparing a solid desulfurizer to solve the problem that the desulfurization effect of the solid desulfurizer basic zinc carbonate prepared in the prior art in drilling fluid needs to be improved.

[0008] The second object of the present invention is to provide a solid desulfurizer to solve the problems of low desulfurization efficiency, flocculation and precipitation in the prior art solid desulfurizers, which affect the rheology and filtration properties of the drilling fluid.

[0009] The third object of the present invention is to provide a solid desulfurizer for use in drilling fluid to solve the problems of low desulfurization efficiency, flocculation and precipitation of solid desulfurizers in the prior art, which affect the rheology and filtration properties of the drilling fluid.

[0010] In order to achieve the above object, the technical solution of a method for preparing a solid desulfurizer in the present invention is:

[0011] A method for preparing a solid desulfurizer comprises reacting a soluble metal salt, dimethylimidazole, and an amino modifier in an organic solvent, and performing solid-liquid separation; the soluble metal salt is a soluble zinc metal salt or a soluble cobalt metal salt; the amino modifier is one of lauryl ammonium sulfate, tetradecylamine, hexadecylamine, octadecylamine, 9-octadecenamine, and 3-triethoxysilyl-1-propylamine; and the mass ratio of the soluble metal salt, dimethylimidazole, and amino modifier is 2-4:4-10:0.2-0.9.

[0012] The beneficial effect of the above technical solution is that the preparation method of the solid desulfurizer of the present invention is a pioneering invention. The present invention utilizes soluble zinc metal salt zinc sulfate hydrate, zinc nitrate hexahydrate or soluble cobalt metal salt cobalt nitrate hexahydrate, cobalt sulfate hexahydrate and dimethylimidazole to react in an organic solvent to generate a metal organic framework material (MOF). Then, under the action of an amino modifier, the aggregation between the generated solid particles is reduced, thereby generating a metal organic framework material with an extremely small particle size, so that it can expose more Co(II) or Zn(II) and NH active sites, which can fully contact with hydrogen sulfide, achieve a rapid and effective desulfurization effect, and prevent the product generated after the reaction from releasing hydrogen sulfide at high temperature, effectively improving the desulfurizer's absorption effect on hydrogen sulfide. The preparation method of the solid desulfurizer of the present invention has a simple operation process and is suitable for large-scale industrial production.

[0013] As a further improvement, the reaction is carried out at room temperature for 8 to 24 hours.

[0014] The beneficial effect of the above technical solution is that the solid desulfurizer of the present invention can be obtained by reacting at room temperature for 8 to 24 hours, which helps to control production costs while ensuring the desulfurization effect of the solid desulfurizer.

[0015] As a further improvement, the particle size of the solid desulfurizer is 10 to 50 nm.

[0016] The beneficial effect of the above technical solution is that the solid desulfurizer prepared by the preparation method of the present invention has a particle size of 10 to 50 nm, can expose more Co(II) or Zn(II) and NH active sites, can fully contact with hydrogen sulfide, and achieve a rapid and effective desulfurization effect.

[0017] As a further improvement, the reaction comprises mixing a soluble zinc metal salt or a soluble cobalt metal salt, dimethylimidazole, and an amino modifier in an organic solvent, ultrasonicating for 10 to 15 minutes, and then reacting at room temperature.

[0018] The beneficial effect of the above technical solution is that ultrasound after mixing the reaction raw materials helps to fully mix the reaction raw materials and improve the rate of subsequent reactions.

[0019] As a further improvement, the organic solvent is methanol; the mass ratio of the dimethylimidazole to methanol is 4-10:240-500.

[0020] In order to achieve the above object, a technical solution of a solid desulfurizer in the present invention is:

[0021] A solid desulfurizer prepared by the solid desulfurizer preparation method.

[0022] The beneficial effects of the above technical solution are as follows: The solid desulfurizer of the present invention is a pioneering invention. The present invention uses a small-particle metal-organic framework material as a solid desulfurizer. Due to the small particle size of the metal-organic framework material, it can expose more Co(II) or Zn(II) and NH active sites, which can fully contact with hydrogen sulfide, achieving a rapid and effective desulfurization effect. It also prevents the products generated after the reaction from releasing hydrogen sulfide at high temperatures, effectively improving the desulfurizer's absorption of hydrogen sulfide. At the same time, the addition of this solid nanomaterial can reduce drilling fluid loss and improve drilling fluid rheology. It can be used in both water-based and oil-based drilling fluids, meeting the needs of on-site drilling desulfurization construction.

[0023] In order to achieve the above object, the technical solution of the application of a solid desulfurizer in drilling fluid in the present invention is:

[0024] Application of a solid desulfurizer in drilling fluid.

[0025] The beneficial effect of the above technical solution is that the application of the solid desulfurizer of the present invention in drilling fluid is a pioneering invention. The present invention adds the solid desulfurizer to the water-based drilling fluid, evaluates its effect on the rheology and filtration, and tests the desulfurization rate at the same time. The results show that the solid desulfurizer of the invention has good performance in water-based drilling fluid, the desulfurization efficiency is greater than 99%, the desulfurization performance is significantly improved, the rheological properties of the drilling fluid are improved, the dynamic-plastic ratio is increased, the rock-carrying effect is enhanced, and the drilling fluid filtration loss is significantly reduced, meeting the on-site desulfurization technology requirements for drilling fluid in high-sulfur formations.

[0026] As a further improvement, the mass content of the solid desulfurizer in the drilling fluid is 0.5-3%.

[0027] The beneficial effect of the above technical solution is that adding the solid desulfurizer to the drilling fluid within the above mass concentration range can effectively control the cost of on-site application while ensuring a good desulfurization effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 The present invention is a flow chart of the preparation method of the solid desulfurizer. DETAILED DESCRIPTION

[0029] The present invention utilizes hydrated zinc sulfate, hexahydrated zinc nitrate, hexahydrated cobalt nitrate, or hexahydrated cobalt sulfate to react with dimethylimidazole in an organic solvent to generate a metal-organic framework (MOF). The metal-organic framework is then modified with an amino modifier to produce a very small particle size. This allows the MOF to expose more Co(II) or Zn(II) and NH active sites, allowing for sufficient contact with hydrogen sulfide, achieving rapid and effective desulfurization. The reaction product is also prevented from releasing hydrogen sulfide at high temperatures, effectively improving the desulfurizer's ability to absorb hydrogen sulfide. The preparation method of the solid desulfurizer of the present invention has a simple operating process and is suitable for large-scale industrial production.

[0030] The preparation process of the solid desulfurizer of the present invention is as follows: Figure 1 shown.

[0031] The present invention will be further described below in conjunction with specific embodiments. It should be noted that, unless otherwise specified, the various embodiments or technical features described below can be arbitrarily combined to form new embodiments. The equipment and raw materials used are all commercially available or commonly used in the art. The methods in the following embodiments are all conventional methods in the art unless otherwise specified.

[0032] In the following examples, unless otherwise specified, the operations described are routine operations in the art.

[0033] In the following examples, unless otherwise specified, all raw materials used are conventional commercial products in the art.

[0034] 1. Specific Examples of the Solid Desulfurizer and Preparation Method of the Present Invention

[0035] Example 1

[0036] The raw materials of the solid desulfurizer of this embodiment are: 3 parts of zinc nitrate hexahydrate, 6 parts of dimethylimidazole, 380 parts of methanol and 0.6 parts of sodium ammonium lauryl sulfate. The specific preparation method is as follows:

[0037] Dissolve 3 parts of zinc nitrate hexahydrate in 180 parts of methanol at room temperature and stir to obtain Liquid A. Dissolve 6 parts of dimethylimidazole and 0.6 parts of ammonium lauryl sulfate in 200 parts of methanol and stir to obtain Liquid B. Quickly pour Liquid A into Liquid B to obtain Liquid C. After ultrasonication for 10 minutes, stir at room temperature for 8 hours. The reaction system is then centrifuged, and the solid product is washed three times with methanol and finally dried in an 80°C oven for 8 hours to obtain a solid product, which is a solid desulfurizer.

[0038] Example 2

[0039] The raw materials of the solid desulfurizer of this embodiment are: 3 parts of cobalt nitrate hexahydrate, 7 parts of dimethylimidazole, 400 parts of methanol and 0.6 parts of 3-triethoxysilyl-1-propylamine. The specific preparation method is as follows:

[0040] Dissolve 3 parts of cobalt nitrate hexahydrate in 200 parts of methanol at room temperature and stir to obtain Liquid A. Dissolve 7 parts of dimethylimidazole and 0.6 parts of 3-triethoxysilyl-1-propylamine in 200 parts of methanol and stir to obtain Liquid B. Liquid A is quickly poured into Liquid B to obtain Liquid C. After ultrasonication for 10 minutes, the mixture is stirred at room temperature for 12 hours. The reaction system is then centrifuged, and the solid product is washed three times with methanol and finally dried in an 80°C oven for 8 hours to obtain a solid product, which is a solid desulfurizer.

[0041] Example 3

[0042] The raw materials of the solid desulfurizer of this embodiment are: 2 parts of zinc sulfate heptahydrate, 4 parts of dimethylimidazole, 500 parts of methanol and 0.9 parts of hexadecylamine. The specific preparation method is as follows:

[0043] Dissolve 2 parts of zinc sulfate heptahydrate in 200 parts of methanol at room temperature and stir to obtain Liquid A. Dissolve 4 parts of dimethylimidazole and 0.9 parts of hexadecylamine in 300 parts of methanol and stir to obtain Liquid B. Quickly pour Liquid A into Liquid B to obtain Liquid C. After ultrasonication for 10 minutes, stir at room temperature for 12 hours. The reaction system is then centrifuged, and the solid product is washed three times with methanol and finally dried in an 80°C oven for 8 hours to obtain a solid product, which is a solid desulfurizer.

[0044] Example 4

[0045] The raw materials of the solid desulfurizer of this embodiment are: 4 parts of cobalt sulfate heptahydrate, 10 parts of dimethylimidazole, 500 parts of methanol and 0.9 parts of octadecylamine. The specific preparation method is as follows:

[0046] Dissolve 4 parts of zinc sulfate heptahydrate in 200 parts of methanol at room temperature and stir to obtain Liquid A. Dissolve 10 parts of dimethylimidazole and 0.9 parts of octadecylamine in 300 parts of methanol and stir to obtain Liquid B. Quickly pour Liquid A into Liquid B to obtain Liquid C. After ultrasonication for 10 minutes, stir at room temperature for 16 hours. The reaction system is then centrifuged, and the solid product is washed three times with methanol and finally dried in an 80°C oven for 8 hours to obtain a solid product, which is a solid desulfurizer.

[0047] Example 5

[0048] The raw materials of the solid desulfurizer of this embodiment are: 3 parts of zinc nitrate hexahydrate, 6 parts of dimethylimidazole, 400 parts of methanol and 0.6 parts of 3-triethoxysilyl-1-propylamine. The specific preparation method is as follows:

[0049] Dissolve 3 parts of zinc sulfate heptahydrate in 200 parts of methanol at room temperature and stir to obtain Liquid A. Dissolve 6 parts of dimethylimidazole and 0.6 parts of 3-triethoxysilyl-1-propylamine in 200 parts of methanol and stir to obtain Liquid B. Quickly pour Liquid A into Liquid B to obtain Liquid C. After ultrasonication for 10 minutes, stir at room temperature for 24 hours. The reaction system is then centrifuged, and the solid product is washed three times with methanol and finally dried in an 80°C oven for 8 hours to obtain a solid product, which is a solid desulfurizer.

[0050] Example 6

[0051] The raw materials of the solid desulfurizer of this embodiment are: 3 parts of cobalt nitrate hexahydrate, 6 parts of dimethylimidazole, 240 parts of methanol and 0.6 parts of octadecylamine. The specific preparation method is as follows:

[0052] Dissolve 3 parts of cobalt nitrate hexahydrate in 120 parts of methanol at room temperature and stir to obtain Liquid A. Dissolve 6 parts of dimethylimidazole and 0.6 parts of octadecylamine in 120 parts of methanol and stir to obtain Liquid B. Quickly pour Liquid A into Liquid B to obtain Liquid C. After ultrasonication for 10 minutes, stir at room temperature for 16 hours. The reaction system is then centrifuged, and the solid product is washed three times with methanol and finally dried in an 80°C oven for 8 hours to obtain a solid product, which is a solid desulfurizer.

[0053] Example 7

[0054] The raw materials of the solid desulfurizer of this embodiment are: 3 parts of cobalt nitrate hexahydrate, 6 parts of dimethylimidazole, 300 parts of methanol and 0.3 parts of octadecylamine. The specific preparation method is as follows:

[0055] Dissolve 3 parts of cobalt nitrate hexahydrate in 150 parts of methanol at room temperature and stir to obtain Liquid A. Dissolve 6 parts of dimethylimidazole and 0.3 parts of octadecylamine in 150 parts of methanol and stir to obtain Liquid B. Quickly pour Liquid A into Liquid B to obtain Liquid C. After ultrasonication for 10 minutes, stir at room temperature for 24 hours. The reaction system is then centrifuged, and the solid product is washed three times with methanol and finally dried in an 80°C oven for 8 hours to obtain a solid product, which is a solid desulfurizer.

[0056] Example 8

[0057] The raw materials of the solid desulfurizer of this embodiment are: 3 parts of zinc nitrate hexahydrate, 6 parts of dimethylimidazole, 480 parts of methanol and 0.2 parts of 3-triethoxysilyl-1-propylamine. The specific preparation method is as follows:

[0058] Dissolve 3 parts of zinc nitrate hexahydrate in 240 parts of methanol at room temperature and stir to obtain Liquid A. Dissolve 6 parts of dimethylimidazole and 0.2 parts of 3-triethoxysilyl-1-propylamine in 240 parts of methanol and stir to obtain Liquid B. Quickly pour Liquid A into Liquid B to obtain Liquid C. After ultrasonication for 10 minutes, stir at room temperature for 24 hours. The reaction system is then centrifuged, and the solid product is washed three times with methanol and finally dried in an 80°C oven for 8 hours to obtain a solid product, which is a solid desulfurizer.

[0059] 2. Comparative Example

[0060] Comparative Example 1

[0061] This comparative example is a commercially available solid desulfurizer, basic zinc carbonate.

[0062] Comparative Example 2

[0063] This comparative example is a 600nm metal organic framework material (MOF-ZIF-8).

[0064] 3. Experimental Example: Application of Solid Desulfurizer in Drilling Fluid

[0065] Experimental Example 1

[0066] This experimental example evaluated the sulfur removal effectiveness of the solid sulfur removers prepared in Examples 1-8 of the present invention and the solid sulfur removers of Comparative Examples 1-2 in drilling fluids. The solid sulfur removers prepared in the present invention and basic zinc carbonate, a commonly available commercial solid sulfur remover, were added to water-based drilling fluids to evaluate their effects on rheology and fluid loss, and to measure sulfur removal efficiency.

[0067] Among them, the water-based drilling fluid formula is: clean water + 4% bentonite + 0.1% soda ash + 0.2% CMC-LV + 0.4% K-PAM + 1% NH4-HPAN + 3% flexible anti-collapse agent + 2.0% emulsified asphalt + 3.0% ultrafine calcium carbonate.

[0068] The evaluation test method is as follows:

[0069] Prepare 400 mL of drilling fluid, add a 1% mass concentration of desulfurizer, and pour it into an aging tank. After sealing, open the tank valve stem and fill the tank with 1 MPa of hydrogen sulfide gas from a 500 ppm hydrogen sulfide cylinder (balanced with nitrogen). The tank is then hot-rolled for 16 hours at 120°C. Based on the standard GB / T 16783.1-2014, the drilling fluid rheology and filtration properties were tested before and after the addition of the desulfurizer. The hydrogen sulfide concentration in the tank after aging was measured using a hydrogen sulfide detector to evaluate the desulfurization efficiency. The test results are shown in Table 1 below.

[0070] Table 1 Drilling fluid properties and desulfurization evaluation results before and after hot rolling

[0071]

[0072] As shown in Table 1, the solid desulfurizer of the present invention performs well in water-based drilling fluids, with a desulfurization efficiency of >99%. This significantly improves the desulfurization performance compared to commonly used commercially available solid desulfurizers, such as basic zinc carbonate and a 600nm metal-organic framework (MOF-ZIF-8). Furthermore, adding the solid desulfurizer of the present invention to drilling fluids improves the rheological properties of the drilling fluid, increases the dynamic-to-plastic ratio, enhances the rock-carrying effect, and significantly reduces fluid loss, meeting the technical requirements for desulfurization of drilling fluids in high-sulfur formations.

[0073] The above description is merely a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by a person skilled in the art within the technical scope disclosed in the embodiments of the present invention should be included in the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be based on the scope of protection of the claims.

Claims

1. A method for preparing a solid desulfurizer, characterized in that: A soluble metal salt, dimethylimidazole, and an amino modifier are reacted in an organic solvent, and solid-liquid separation is performed; the soluble metal salt is a soluble zinc metal salt or a soluble cobalt metal salt; the amino modifier is one of lauryl ammonium sulfate, tetradecylamine, hexadecylamine, octadecylamine, 9-octadecenamine, and 3-triethoxysilyl-1-propylamine; and the mass ratio of the soluble metal salt, dimethylimidazole, and amino modifier is 2-4:4-10:0.2-0.

9.

2. The method for preparing a solid desulfurizer according to claim 1, wherein: The reaction is carried out at room temperature for 8 to 24 hours.

3. The method for preparing a solid desulfurizer according to claim 1, wherein: The particle size of the solid desulfurizer is 10 to 50 nm.

4. The method for preparing a solid desulfurizer according to claim 2, wherein: The reaction comprises mixing a soluble zinc metal salt or a soluble cobalt metal salt, dimethyl imidazole and an amino modifier in an organic solvent, ultrasonicating for 10 to 15 minutes, and then reacting at room temperature.

5. The method for preparing a solid desulfurizing agent according to any one of claims 1 to 4, characterized in that: The organic solvent is methanol; the mass ratio of the dimethylimidazole to methanol is 4-10:240-500.

6. A solid desulfurizer prepared by the method for preparing a solid desulfurizer according to any one of claims 1 to 5.

7. Use of the solid desulfurizer according to claim 6 in drilling fluid.

8. Use of the solid desulfurizer in drilling fluid according to claim 7, characterized in that: The mass content of the solid desulfurizer in the drilling fluid is 0.5-3%.

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