Crosslinked composite sulfur removal agent and preparation method thereof

Abstract

The invention relates to the technical field of sulfur removal agents, in particular to a cross-linked composite sulfur removal agent and a preparation method thereof, and the cross-linked composite sulfur removal agent is prepared according to the following steps: mixing required amount of alcohol amine and aldehyde for reaction to obtain a monocyclic triazine aqueous solution, and dehydrating and purifying the monocyclic triazine aqueous solution to obtain the cross-linked composite sulfur removal agent. Sequentially adding a required amount of dicarboxylic acid, high carbonic acid, a catalyst and xylene into a part of the required amount of purified monocyclic triazine aqueous solution, reacting to obtain a cross-linked and oil-soluble sulfur removal agent, then adding the cross-linked and oil-soluble sulfur removal agent and an emulsifier into the other part of the required amount of purified monocyclic triazine aqueous solution, uniformly stirring, and standing to obtain the cross-linked and oil-soluble sulfur removal agent. The cross-linked composite sulfur removal agent is obtained. According to the cross-linked composite sulfur removal agent obtained by the invention, polycyclic azide is realized, on one hand, hydrogen sulfide in oil can be effectively removed, and the sulfur content in oil-water produced liquid is further reduced, so that the cross-linked composite sulfur removal agent has efficient sulfur removal capacity, and on the other hand, the consumption of the sulfur removal agent is reduced, and the sulfur removal cost of oil and gas field sewage is reduced.

Description

Technical Field

[0001] The invention relates to the technical field of desulfurizers and relates to a cross-linked composite desulfurizer and a preparation method thereof. Background Art

[0002] The transportation of sulfur-containing wastewater from natural gas mines is characterized by large volume, long distance and high risk. Gas field wastewater is generally purified and reinjected through filters, booster pumps, water injection pumps and other equipment. In these processes, pipelines and equipment are often corroded, seriously affecting normal production and causing huge economic losses. Some areas use centralized transportation to solve the problem. Once leakage occurs during transportation, coupled with dissolved substances such as hydrogen sulfide in the water, it may lead to serious environmental accidents such as pollution of drinking water sources and even the risk of poisoning of surrounding personnel. Hydrogen sulfide is a highly irritating gas with a strong smell of rotten eggs. The presence of hydrogen sulfide in the production process of oil and gas wells will not only cause corrosion of equipment and pipelines, catalyst poisoning, but also seriously threaten personal safety.

[0003] The Chinese patent document with the publication number CN117164530A discloses a polycyclic azide desulfurizer and a synthesis method thereof, comprising the following steps: mixing alcohol amine and amide, stirring and heating evenly, dropping a catalyst, and obtaining a monocyclic triazine after reaction; taking the monocyclic azide compound obtained by the reaction and heating it, adding polyaldehyde, mixing and stirring evenly, dropping a catalyst, stirring to achieve a coupling reaction; or mixing a small molecule aldehyde and amide, stirring and heating evenly, dropping a catalyst for reaction, adding amide, dropping a catalyst, stirring to achieve a coupling reaction; separating the byproducts from the obtained product after the coupling reaction, and purifying. The polytriazine rings of the desulfurizer can achieve a high monomer desulfurization rate, effectively reduce the sulfur content in sewage, and the generated product is soluble in water and will not affect normal production.

[0004] It can be seen that triazine desulfurizers have good desulfurization efficiency, are easy to prepare industrially, the product is soluble in water, low toxicity, has bactericidal properties, can reduce equipment corrosion, are environmentally friendly, have low equipment requirements during industrial use, are easy to operate, and have low costs. However, in the field implementation process, a single water-soluble desulfurizer is usually used. Although this method can effectively reduce water, because the desulfurizer cannot enter the oil phase, the treatment effect is slow, and the hydrogen sulfide content in the treated crude oil is high. Summary of the invention

[0005] The present invention provides a cross-linked composite desulfurizer and a preparation method thereof, which overcomes the deficiencies of the above-mentioned prior art and can effectively solve the problem that the prior desulfurizer cannot enter the oil phase, resulting in slow desulfurization effect and low desulfurization capacity, thereby resulting in large amount of desulfurizer used and high desulfurization cost.

[0006] One of the technical solutions of the present invention is achieved by the following measures: A method for preparing a cross-linked composite desulfurizer is carried out according to the following steps: S1, mixing a required amount of alcohol amine and aldehyde to react to obtain a monocyclic triazine aqueous solution; S2, after dehydrating and purifying the monocyclic triazine aqueous solution, adding a required amount of dicarboxylic acid, high carbonic acid, catalyst and xylene to a required amount of the purified monocyclic triazine aqueous solution in sequence, reacting to obtain a cross-linked and oil-soluble desulfurizer; S3, adding a cross-linked and oil-soluble desulfurizer and an emulsifier to another required amount of the purified monocyclic triazine aqueous solution, stirring evenly, to obtain a cross-linked composite desulfurizer.

[0007] The following is a further optimization and / or improvement of one of the above-mentioned technical solutions: In the above step S1, the molar ratio of the alcoholamine to the aldehyde is 1:1.

[0008] In the above step S1, the alcoholamine is monoethanolamine, and the aldehyde is formaldehyde.

[0009] In the above step S1, the reaction temperature is 60°C and the reaction time is 3.0h.

[0010] In the above step S2, the molar ratio of the carboxylic acid group in the dicarboxylic acid to the added purified monocyclic triazine aqueous solution is 1:1 to 2, the molar ratio of the percarbonate to the added purified monocyclic triazine aqueous solution is 1:1 to 2, and the amount of the catalyst added is 0.4% to 2.5% of the mass of the added purified monocyclic triazine aqueous solution.

[0011] In the above step S2, the dicarboxylic acid is one of adipic acid and glutaric acid, the percarbonic acid is one or more of dodecanoic acid, tetradecanoic acid, hexadecanoic acid, and octadecanoic acid, and the catalyst is one or more of dodecylbenzenesulfonic acid, p-toluenesulfonic acid, and aminosulfonic acid.

[0012] In the above step S2, the reaction temperature is 120°C to 150°C, and the reaction time is 2.0h to 10.0h.

[0013] In the above step S3, the mass ratio of the purified monocyclic triazine aqueous solution to the cross-linked and oil-soluble desulfurizer is 1:0.2 to 1.0.

[0014] In the above step S3, the emulsifier is one or more of sodium lauryl sulfate, diethylene glycol monostearate, fatty alcohol polyoxyethylene ether, polyethylene glycol dilaurate, and polyglycerol ricinoleate, wherein the amount of the emulsifier added is 1% to 15% of the mass of the monocyclic triazine aqueous solution.

[0015] The second technical solution of the present invention is achieved through the following measures: a cross-linked composite desulfurizer is prepared by a preparation method of a cross-linked composite desulfurizer.

[0016] The cross-linked composite desulfurizer obtained by the present invention realizes polycyclic azide, which can effectively remove hydrogen sulfide in oil and further reduce the sulfur content in oil-water produced fluid, and has a high desulfurization capacity. On the other hand, it also reduces the amount of desulfurizer used and reduces the desulfurization cost of oil and gas field wastewater. DETAILED DESCRIPTION

[0017] The present invention is not limited by the following embodiments, and the specific implementation method can be determined according to the technical scheme of the present invention and the actual situation. Unless otherwise specified, the various chemical reagents and chemicals mentioned in the present invention are all chemical reagents and chemicals known and used in the prior art; unless otherwise specified, the percentages in the present invention are all mass percentages; unless otherwise specified, the solutions in the present invention are all aqueous solutions with water as the solvent, for example, hydrochloric acid solution is a hydrochloric acid aqueous solution; the normal temperature and room temperature in the present invention generally refer to a temperature of 15°C to 25°C, and are generally defined as 25°C.

[0018] The present invention will be further described below in conjunction with embodiments: Example 1: The preparation method of the cross-linked composite desulfurizer is carried out according to the following steps: S1, mixing a required amount of alcohol amine and aldehyde to react to obtain a monocyclic triazine aqueous solution; S2, after dehydrating and purifying the monocyclic triazine aqueous solution, adding a required amount of dicarboxylic acid, high carbonic acid, catalyst and xylene to a required amount of the purified monocyclic triazine aqueous solution in sequence, reacting to obtain a cross-linked and oil-soluble desulfurizer; S3, adding a cross-linked and oil-soluble desulfurizer and an emulsifier to another required amount of the purified monocyclic triazine aqueous solution, stirring evenly, to obtain a cross-linked composite desulfurizer.

[0019] Example 2: As an optimization of the above example, in step S1, the molar ratio of the alcoholamine to the aldehyde is 1:1.

[0020] Example 3: As an optimization of the above example, in step S1, the alcoholamine is monoethanolamine, and the aldehyde is formaldehyde.

[0021] Example 4: As an optimization of the above example, in step S1, the reaction temperature is 60°C and the reaction time is 3.0h.

[0022] Example 5: As an optimization of the above example, in step S2, the molar ratio of the carboxylic acid group in the dicarboxylic acid to the added purified monocyclic triazine aqueous solution is 1:1 to 2, the molar ratio of high carbonic acid to the added purified monocyclic triazine aqueous solution is 1:1 to 2, and the amount of catalyst added is 0.4% to 2.5% of the mass of the added purified monocyclic triazine aqueous solution.

[0023] Example 6: As an optimization of the above example, in step S2, the dicarboxylic acid is one of adipic acid and glutaric acid, the percarbonic acid is one or more of dodecanoic acid, tetradecanoic acid, hexadecanoic acid, and octadecanoic acid, and the catalyst is one or more of dodecylbenzenesulfonic acid, p-toluenesulfonic acid, and aminosulfonic acid.

[0024] Example 7: As an optimization of the above example, in step S2, the reaction temperature is 120°C to 150°C, and the reaction time is 2.0h to 10.0h.

[0025] Example 8: As an optimization of the above example, in step S3, the mass ratio of the purified monocyclic triazine aqueous solution to the cross-linked and oil-soluble desulfurizer is 1:0.2 to 1.0.

[0026] Example 9: As an optimization of the above example, in step S3, the emulsifier is one or more of sodium lauryl sulfate, diethylene glycol monostearate, fatty alcohol polyoxyethylene ether, polyethylene glycol dilaurate, and polyglycerol ricinoleate, wherein the amount of the emulsifier added is 1% to 15% of the mass of the monocyclic triazine aqueous solution.

[0027] Example 10: The cross-linked composite desulfurizer prepared by the preparation method of the cross-linked composite desulfurizer.

[0028] Example 11: The cross-linked composite desulfurizer is prepared according to the following steps: S1, add all 1830kg of monoethanolamine into the kettle, turn on the stirring device and adjust the speed to 100rpm, turn on the heating device, control the temperature to 60°C, open the constant pressure dripping tank containing formaldehyde, slowly adjust the dripping speed of formaldehyde, add a total of 2500kg of formaldehyde, react at 60°C for 3h, and obtain a monocyclic triazine aqueous solution; S2, taking 1210 kg of purified monocyclic triazine aqueous solution, adding 80 kg of adipic acid, 5 kg of aminosulfonic acid, 200 kg of octadecanoic acid, adding 1200 kg of xylene (solvent), controlling the temperature at 140°C to react for 6 hours, and obtaining a cross-linked and oil-soluble desulfurizer; S3, taking 500 kg of the purified monocyclic triazine aqueous solution, adding 10 kg of sodium dodecyl sulfate, 2 kg of diethylene glycol monostearate, and 500 kg of a cross-linked and oil-soluble desulfurizer, and stirring evenly to obtain a cross-linked composite desulfurizer.

[0029] Example 12: The cross-linked composite desulfurizer is prepared according to the following steps: S1, add all 1830kg of monoethanolamine into the kettle, turn on the stirring device and adjust the speed to 100rpm, turn on the heating device, control the temperature to 60°C, open the constant pressure dripping tank containing formaldehyde, slowly adjust the dripping speed of formaldehyde, add a total of 2500kg of formaldehyde, react at 60°C for 3h, and obtain a monocyclic triazine aqueous solution; S2, take 1210kg of the purified monocyclic triazine aqueous solution, add 80kg of glutaric acid, 5kg of aminosulfonic acid, 200kg of octadecanoic acid, add 1200kg of xylene (solvent), control the temperature at 150℃ and react for 2h to obtain a cross-linked and oil-soluble desulfurizer; S3, taking 500 kg of the purified monocyclic triazine aqueous solution, adding 10 kg of sodium dodecyl sulfate, 2 kg of diethylene glycol monostearate, and 500 kg of a cross-linked and oil-soluble desulfurizer, and stirring evenly to obtain a cross-linked composite desulfurizer.

[0030] Example 13: The cross-linked composite desulfurizer is prepared according to the following steps: S1, add all 1830kg of monoethanolamine into the kettle, turn on the stirring device and adjust the speed to 100rpm, turn on the heating device, control the temperature to 60°C, open the constant pressure dripping tank containing formaldehyde, slowly adjust the dripping speed of formaldehyde, add a total of 2500kg of formaldehyde, react at 60°C for 3h, and obtain a monocyclic triazine aqueous solution; S2, take 1210kg of the purified monocyclic triazine aqueous solution, add 80kg of adipic acid, 5kg of p-toluenesulfonic acid, 200kg of octadecanoic acid, add 1200kg of xylene (solvent), control the temperature at 120℃ and react for 10h to obtain a cross-linked and oil-soluble desulfurizer; S3, taking 500 kg of the purified monocyclic triazine aqueous solution, adding 10 kg of sodium dodecyl sulfate, 2 kg of fatty alcohol polyoxyethylene ether, and 500 kg of a cross-linked and oil-soluble desulfurizer, stirring evenly, to obtain a cross-linked composite desulfurizer.

[0031] Example 14: The cross-linked composite desulfurizer is prepared according to the following steps: S1, add all 1830kg of monoethanolamine into the kettle, turn on the stirring device and adjust the speed to 600rpm, turn on the heating device, control the temperature to 60°C, open the constant pressure dripping tank containing formaldehyde, slowly adjust the dripping speed of formaldehyde, add a total of 2500kg of formaldehyde, react at 60°C for 3h, and obtain a monocyclic triazine aqueous solution; S2, take 1210kg of the purified monocyclic triazine aqueous solution, add 80kg of adipic acid, 5kg of aminosulfonic acid, 200kg of hexadecanoic acid, add 1200kg of xylene (solvent), control the temperature at 130℃ and react for 8h to obtain a cross-linked and oil-soluble desulfurizer; S3, taking 500 kg of the purified monocyclic triazine aqueous solution, adding 10 kg of sodium dodecyl sulfate, 2 kg of diethylene glycol monostearate, and 500 kg of a cross-linked and oil-soluble desulfurizer, and stirring evenly to obtain a cross-linked composite desulfurizer.

[0032] Example 15: The cross-linked composite desulfurizer is prepared according to the following steps: S1, add all 1830kg of monoethanolamine into the kettle, turn on the stirring device and adjust the speed to 600rpm, turn on the heating device, control the temperature to 60°C, open the constant pressure dripping tank containing formaldehyde, slowly adjust the dripping speed of formaldehyde, add a total of 2500kg of formaldehyde, react at 60°C for 3h, and obtain a monocyclic triazine aqueous solution; S2, take 1210kg of the purified monocyclic triazine aqueous solution, add 80kg of adipic acid, 5kg of aminosulfonic acid, 200kg of dodecanoic acid, add 1200kg of xylene (solvent), control the temperature at 140℃ and react for 6h to obtain a cross-linked and oil-soluble desulfurizer; S3, taking 500 kg of the purified monocyclic triazine aqueous solution, adding 10 kg of sodium dodecyl sulfate, 2 kg of diethylene glycol monostearate, and 500 kg of a cross-linked and oil-soluble desulfurizer, and stirring evenly to obtain a cross-linked composite desulfurizer.

[0033] Example 16: The cross-linked composite desulfurizer is prepared according to the following steps: S1, add all 1830kg of monoethanolamine into the kettle, turn on the stirring device and adjust the speed to 600rpm, turn on the heating device, control the temperature to 60°C, open the constant pressure dripping tank containing formaldehyde, slowly adjust the dripping speed of formaldehyde, add a total of 2500kg of formaldehyde, react at 60°C for 3h, and obtain a monocyclic triazine aqueous solution; S2, take 1210kg of the purified monocyclic triazine aqueous solution, add 80kg of adipic acid, 5kg of aminosulfonic acid, 200kg of octadecanoic acid, add 1200kg of xylene (solvent), control the temperature at 140℃ and react for 6h to obtain a cross-linked and oil-soluble desulfurizer; S3, taking 500 kg of the purified monocyclic triazine aqueous solution, adding 10 kg of sodium dodecyl sulfate, 2 kg of polyethylene glycol dilaurate, and 500 kg of a cross-linked and oil-soluble desulfurizer, and stirring evenly to obtain a cross-linked composite desulfurizer.

[0034] Comparative Example 1: The monocyclic triazine aqueous solution obtained in step S1 of Example 11 was used as a desulfurizing agent.

[0035] Comparative Example 2: The cross-linked and oil-soluble desulfurizer obtained in step S2 of Example 11 was used as the desulfurizer.

[0036] The performance test of the cross-linked composite desulfurizer obtained in Examples 11 to 16 was carried out The oil-water produced liquid from the oil field was used to perform an oil removal performance evaluation experiment using the cross-linked composite desulfurizer obtained in Examples 11 to 16 and the desulfurizer obtained in Comparative Examples 1 and 2, respectively, to examine the effects of the agents on the desulfurization performance at the same dosage concentration. The specific evaluation method is as follows: Take 1L of the oil-water mixture sample from the site, put it in a closed container, and then heat it to 60°C to test the content of hydrogen sulfide in the gas phase. The results are shown in Table 1. 1L of the oil-water mixture sample was taken from the site, 500ppm of each cross-linked composite desulfurizer obtained in Examples 11 to 16 was added, the mixture was placed in a sealed container, and then the temperature was raised to 60°C. The hydrogen sulfide content in the gas phase was tested. The results are shown in Table 1.

[0037] 1L of the oil-water mixture sample was taken on site, 500ppm of the desulfurizers obtained in Comparative Examples 1 and 2 were added, the mixture was placed in a sealed container, and then the temperature was raised to 60°C. The hydrogen sulfide content in the gas phase was tested. The results are shown in Table 1.

[0038] Table 1 .

[0039] As shown in Table 1, from the comparison between Example 11 and Example 12, Example 13 and Example 16, it can be seen that different catalysts, cross-linking agents and emulsifiers have little effect on the performance of the product formula.

[0040] From the comparison of Example 11, Example 14, and Example 15, it can be seen that the different carbon chain lengths of the added high carbonic acid have a certain influence on the performance of the desulfurizer. Mainly, when the carbon chain is shorter, it affects the dissolution and diffusion of the oily desulfurizer in the oil. It can be seen that the cross-linked and oil-soluble desulfurizer with 18 carbon atoms in the added high carbonic acid has the best effect.

[0041] It can be seen that for the oil-water mixture, the effects of using a single oil-soluble desulfurizer (Comparative Example 2) and a single water-soluble desulfurizer (Comparative Example 1) are relatively poor. The cross-linked composite desulfurizer of the present invention can effectively remove sulfides in the liquid phase.

[0042] In summary, the cross-linked composite desulfurizer obtained by the present invention realizes polycyclic azide, which can effectively remove hydrogen sulfide in oil and further reduce the sulfur content in oil-water produced fluid, and has efficient desulfurization ability. On the other hand, it also reduces the amount of desulfurizer used and reduces the desulfurization cost of oil and gas field wastewater.

[0043] The above technical features constitute the embodiments of the present invention, which have strong adaptability and implementation effect. Non-essential technical features can be added or reduced according to actual needs to meet the requirements of different situations.

Claims

1. A method for preparing a cross-linked composite desulfurizer, characterized in that Follow the steps below: S1, mixing a required amount of alcohol amine and aldehyde to react to obtain a monocyclic triazine aqueous solution; S2, after dehydrating and purifying the monocyclic triazine aqueous solution, adding a required amount of dicarboxylic acid, high carbonic acid, catalyst and xylene to a required amount of the purified monocyclic triazine aqueous solution in sequence, reacting to obtain a cross-linked and oil-soluble desulfurizer; S3, adding a cross-linked and oil-soluble desulfurizer and an emulsifier to another required amount of the purified monocyclic triazine aqueous solution, stirring evenly, to obtain a cross-linked composite desulfurizer.

2. The method for preparing the cross-linked composite desulfurizer according to claim 1, characterized in that In step S1, the molar ratio of the alcoholamine to the aldehyde is 1:

1.

3. The method for preparing the cross-linked composite desulfurizer according to claim 1 or 2, characterized in that In step S1, the alcoholamine is monoethanolamine, and the aldehyde is formaldehyde.

4. The method for preparing the cross-linked composite desulfurizer according to claim 3, characterized in that In step S1, the reaction temperature is 60° C. and the reaction time is 3.0 h.

5. The method for preparing a cross-linked composite desulfurizer according to claim 1, 2 or 4, characterized in that In step S2, the molar ratio of the carboxylic acid group in the dicarboxylic acid to the added purified monocyclic triazine aqueous solution is 1:1 to 2, the molar ratio of the percarbonate to the added purified monocyclic triazine aqueous solution is 1:1 to 2, and the amount of the catalyst added is 0.4% to 2.5% of the mass of the added purified monocyclic triazine aqueous solution.

6. The method for preparing the cross-linked composite desulfurizer according to claim 5, characterized in that In step S2, the dicarboxylic acid is one of adipic acid and glutaric acid, the percarbonic acid is one or more of dodecanoic acid, tetradecanoic acid, hexadecanoic acid, and octadecanoic acid, and the catalyst is one or more of dodecylbenzenesulfonic acid, p-toluenesulfonic acid, and aminosulfonic acid.

7. The method for preparing a cross-linked composite desulfurizer according to claim 1, 2, 4 or 6, characterized in that In step S2, the reaction temperature is 120°C to 150°C, and the reaction time is 2.0h to 10.0h.

8. The method for preparing the cross-linked composite desulfurizer according to claim 7, characterized in that In step S3, the mass ratio of the purified monocyclic triazine aqueous solution to the cross-linked and oil-soluble desulfurizer is 1:0.2 to 1.

0.

9. The method for preparing a cross-linked composite desulfurizer according to claim 1, 2, 4, 6 or 8, characterized in that In step S3, the emulsifier is one or more of sodium lauryl sulfate, diethylene glycol monostearate, fatty alcohol polyoxyethylene ether, polyethylene glycol dilaurate, and polyglycerol ricinoleate, wherein the amount of the emulsifier added is 1% to 15% of the mass of the monocyclic triazine aqueous solution.

10. A cross-linked composite desulfurizer prepared according to the method for preparing a cross-linked composite desulfurizer according to any one of claims 1 to 9.