Triazine desulfurizer as well as preparation method and application thereof

Abstract

The invention discloses a triazine desulfurizer as well as a preparation method and application thereof, and relates to the technical field of petrochemical engineering. The triazine desulfurizing agent prepared by the invention comprises the composite triazine methoxazole, the oxazolidine tetraformate and the additive, the composite triazine methoxazole is prepared by reacting sulfamethoxazole with paraformaldehyde and then mixing with fatty alcohol-polyoxyethylene ether, the desulfurization rate is improved, the reaction temperature of the triazine desulfurizing agent can also be improved, and the desulfurization efficiency is improved. The oxazolidine tetraformate is prepared by reacting diethyl malonate with 1, 3-bromopropane and then reacting with hydroxyethyl oxazolidine, and the hydroxyethyl oxazolidine is prepared by reacting diethanol amine with acetone, so that the compatibility with crude oil is further enhanced, and the desulfurization rate is increased.

Description

Technical Field

[0001] The present invention relates to the technical field of petrochemical engineering, and particularly to a triazine desulfurizer, a preparation method thereof, and an application thereof. Background Art

[0002] With the development of the economy, the demand for energy continues to grow, and the crude oil extraction shows a trend of high sulfur content. The sulfide content in crude oil is relatively high. Sulfides have the characteristics of stench, high toxicity, and strong corrosiveness. Their presence in crude oil brings serious safety problems to both oilfield production and oil and gas gathering and transportation. In recent years, chemical desulfurizers have been widely used due to their advantages of small addition amount and convenient operation.

[0003] When the triazine desulfurizer removes hydrogen sulfide in crude oil, after the first nitrogen on the triazine ring participates in the reaction, it is difficult for the second and third nitrogens on the triazine ring to participate in the reaction. Therefore, the desulfurization rate of the above triazine desulfurizer needs to be further improved. Therefore, the present invention has studied a triazine desulfurizer with a relatively high desulfurization rate for crude oil desulfurization. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a triazine desulfurizer, a preparation method thereof, and an application thereof.

[0005] A technical solution proposed by the present invention to solve the above technical problem is: a triazine desulfurizer, including compound triazine methyl oxazole, tetracarboxylic acid oxazolidine, and an additive; the compound triazine methyl oxazole is prepared by reacting sulfamethoxazole with paraformaldehyde and then mixing with fatty alcohol polyoxyethylene ether.

[0006] Preferably, the tetracarboxylic acid oxazolidine is prepared by reacting diethyl diethylmalonate with 1,3-bromopropane and then reacting with hydroxyethyl oxazolidine.

[0007] Preferably, the hydroxyethyl oxazolidine is prepared by reacting diethanolamine with acetone.

[0008] Preferably, the additive is one of ferric sulfate or ferric acetate.

[0009] Preferably, the preparation method of the triazine desulfurizer includes the following specific steps: S1. Heat formaldehyde to 35-45°C, add an equal mass of sulfamethoxazole, and dropwise add sulfuric acid with a mass fraction of 3-5% and 0.2-0.4 times the mass of formaldehyde at a rate of 1-3 ml / min. Keep the temperature for reaction for 8-10 h, and carry out vacuum distillation to obtain triazine methyl oxazole: S2. Mix triazine methyl oxazole and fatty alcohol polyoxyethylene ether according to a mass ratio of 20:1-3, heat to 50-60°C, and stir at 200-400 rpm for 8-10 min to obtain compound triazine methyl oxazole: S3. Under a nitrogen atmosphere, sodium ethoxide, tetraethyl pyromellitate, and hydroxyethyl oxazolidine are mixed in a mass ratio of 3:8:20 - 22. After stirring evenly, the temperature is raised to 105 - 115°C. After refluxing for 3 - 4 hours, the pressure is reduced to 8 - 10 kPa, and the reaction continues for 3 - 4 hours. Then the temperature is raised to 120 - 130°C, and p-toluenesulfonic acid with a mass 3 - 5 times that of sodium ethoxide and butanone with a mass 0.02 - 0.04 times that of sodium ethoxide are added during vacuum distillation. After stirring evenly, calcium oxide with a mass 0.15 - 0.25 times that of sodium ethoxide is added, and the reaction proceeds for 1 - 2 hours. Then it is transferred to a drying oven at 70 - 80°C for drying to obtain oxazolidine tetracarboxylic acid; S4. The compound triazine methyloxazole, oxazolidine tetracarboxylic acid, and an additive are mixed, and the temperature is raised to 45 - 55°C and stirred evenly to obtain a triazine-based desulfurizer.

[0010] Preferably, in the above step S3, the preparation method of hydroxyethyl oxazolidine is as follows: Toluene and diethanolamine are mixed in a mass ratio of 2:1 - 1.04. After stirring evenly, the temperature is raised to 40 - 42°C, and acetone with a mass 1.1 - 1.3 times that of diethanolamine is added dropwise at a rate of 1 - 3 ml / min. The reaction proceeds for 1 - 2 hours, then the temperature is raised to 60 - 62°C, and the reflux reaction continues for 3 - 5 hours. After cooling to room temperature, vacuum fractionation is carried out, and the fraction at 65°C is collected to obtain hydroxyethyl oxazolidine.

[0011] Preferably, in the above step S4, the mass ratio of the compound triazine methyloxazole, oxazolidine tetracarboxylic acid, and the additive is 50 - 60:10 - 20:3 - 8.

[0012] Preferably, the triazine-based desulfurizer is applied to the desulfurization of crude oil.

[0013] Compared with the prior art, the beneficial effects achieved by the present invention are as follows: The triazine-based desulfurizer prepared by the present invention includes compound triazine methyloxazole, oxazolidine tetracarboxylic acid, and an additive; The compound triazine methyloxazole is prepared by reacting sulfamethoxazole with paraformaldehyde and then mixing with fatty alcohol polyoxyethylene ether. Sulfamethoxazole and paraformaldehyde undergo an amino - aldehyde condensation to form triazine methyloxazole with a benzene ring side chain, increasing the compatibility with crude oil and enabling sufficient contact with sulfur - containing substances in the crude oil, thereby improving the desulfurization rate. It can also increase the reaction temperature of the triazine desulfurizer and has a higher applicable temperature. Then, it is mixed with the surfactant fatty alcohol polyoxyethylene ether to reduce the surface tension of the system, further enhancing the compatibility between the triazine desulfurizer and crude oil, and further improving the desulfurization rate; Oxazolidine tetracarboxylic acid is prepared by reacting diethyl diethylmalonate with 1,3-dibromopropane and then reacting with hydroxyethyl oxazolidine. Hydroxyethyl oxazolidine is prepared by reacting diethanolamine and acetone. Diethanolamine and acetone react to form oxazolidine with a hydroxyethyl group, which then reacts with tetraethyl tetracarboxylate with a terminal tetracarboxylic acid group formed by the reaction of diethyl diethylmalonate and 1,3-dibromopropane to obtain oxazolidine tetracarboxylic acid with a symmetric structure. The oxazolidine tetracarboxylic acid with a higher functionality further enhances the compatibility with crude oil and improves the desulfurization rate. Detailed implementation mode

[0014] The present invention will be specifically described below through examples. It is necessary to point out here that the following examples are only used to further illustrate the present invention and cannot be understood as limiting the protection scope of the present invention. Those skilled in the art can make some non-essential improvements and adjustments to the present invention according to the above content of the present invention. Unless otherwise defined, all professional and scientific terms used herein have the same meaning as those familiar to those skilled in the art.

[0015] In order to more clearly illustrate the method provided by the present invention, the following examples are used for detailed description. The test methods for each index of the highly stain-resistant hot-melt marking materials prepared in the examples and comparative examples are as follows: Desulfurization rate: The triazine-based desulfurizing agents prepared in the examples and comparative examples were added to the same mass of crude oil at an addition amount of 200 mg / L, and desulfurized for 60 minutes at 30 °C, 60 °C and 90 °C respectively, and the hydrogen sulfide concentration before and after desulfurization was measured. Example

[0016] The preparation method of the triazine-based desulfurizing agent in this example is as follows: S1. Heat formaldehyde to 35 °C, add an equal mass of sulfamethoxazole, and dropwise add sulfuric acid with a mass fraction of 3% and 0.2 times the mass of formaldehyde at a rate of 1 ml / min. Keep the temperature for reaction for 8 h and perform vacuum distillation to obtain triazine sulfamethoxazole: S2. Mix triazine sulfamethoxazole and fatty alcohol polyoxyethylene ether in a mass ratio of 20:1, heat to 50 °C, and stir at 200 rpm for 8 min to obtain composite triazine sulfamethoxazole: S3. Mix toluene and diethanolamine at a mass ratio of 2:1. After stirring evenly, heat it up to 40 °C, and dropwise add acetone which is 1.1 times the mass of diethanolamine at a rate of 1 ml / min. React for 1 h, then heat it up to 60 °C and reflux for 3 h. After cooling to room temperature, carry out vacuum fractional distillation and collect the fraction at 65 °C to obtain hydroxyethyl oxazolidine; Under a nitrogen atmosphere, mix sodium and absolute ethanol at a mass ratio of 1:20. After stirring and dissolving, add diethyl diethylmalonate which is 8 times the mass of sodium. After reacting for 4 h, dropwise add 1,3-bromopropane at a rate of 1 ml / min, heat it up to 60 °C and reflux for 14 h, carry out vacuum distillation, then add sulfuric acid with a mass fraction of 3% which is 0.2 times the mass of sodium. After standing and separating layers, extract with ethyl acetate, dry with anhydrous magnesium sulfate, and carry out column chromatography separation with petroleum ether and ethyl acetate with a volume ratio of 20:1 after vacuum distillation to obtain tetraethyl endo-tetracarboxylate; Under a nitrogen atmosphere, mix sodium ethoxide, tetraethyl endo-tetracarboxylate and hydroxyethyl oxazolidine at a mass ratio of 3:8:20. After stirring evenly, heat it up to 105 °C and reflux for 3 h, then reduce the pressure to 8 kPa and continue to react for 3 h. Heat it up to 120 °C, carry out vacuum distillation and then add p-toluenesulfonic acid which is 3 times the mass of sodium ethoxide and methyl ethyl ketone which is 0.02 times the mass of sodium ethoxide. After stirring evenly, add calcium oxide which is 0.15 times the mass of sodium ethoxide and react for 1 h. Transfer it to a drying oven at 70 °C for drying to obtain oxazolidine tetracarboxylic acid; S4. Mix compound triazine methyloxazole, oxazolidine tetracarboxylic acid and additive ferric sulfate at a mass ratio of 50:10:3, heat it up to 45 °C and stir evenly to obtain a triazine desulfurizer. Example

[0017] The preparation method of the triazine desulfurizer in this example is as follows: S1. Heat formaldehyde to 40 °C, add sulfamethoxazole of equal mass, and dropwise add sulfuric acid with a mass fraction of 4% which is 0.3 times the mass of formaldehyde at a rate of 2 ml / min. Keep the temperature for reaction for 9 h and carry out vacuum distillation to obtain triazine methyloxazole: S2. Mix triazine methyloxazole and fatty alcohol polyoxyethylene ether at a mass ratio of 20:1~3, heat it up to 55 °C and stir at 300 rpm for 9 min to obtain compound triazine methyloxazole: S3. Mix toluene and diethanolamine at a mass ratio of 2:1.02, stir evenly and then heat up to 41°C. Dropwise add acetone which is 1.2 times the mass of diethanolamine at a rate of 2 ml / min, react for 1.5 h, then heat up to 61°C and reflux for 3 - 5 h. After cooling to room temperature, perform vacuum fractional distillation and collect the fraction at 65°C to obtain hydroxyethyl oxazolidine; Under a nitrogen atmosphere, mix sodium and absolute ethanol at a mass ratio of 1.1:20, stir to dissolve and then add diethyl diethylmalonate which is 9 times the mass of sodium. After reacting for 5 h, dropwise add 1,3 - bromopropane at a rate of 2 ml / min, heat up to 65°C and reflux for 15 h. Perform vacuum distillation, then add sulfuric acid with a mass fraction of 4% which is 0.4 times the mass of sodium. After standing and separating layers, extract with ethyl acetate, dry with anhydrous magnesium sulfate, and perform column chromatography separation with petroleum ether and ethyl acetate in a volume ratio of 20:1 after vacuum distillation to obtain tetraethyl end - tetracarboxylate; Under a nitrogen atmosphere, mix sodium ethoxide, tetraethyl end - tetracarboxylate and hydroxyethyl oxazolidine at a mass ratio of 3:8:21, stir evenly, heat up to 110°C, reflux for 3.5 h, then reduce the pressure to 9 kPa and continue to react for 3.5 h. Heat up to 125°C, perform vacuum distillation and then add p - toluenesulfonic acid which is 4 times the mass of sodium ethoxide and methyl ethyl ketone which is 0.03 times the mass of sodium ethoxide. Stir evenly and then add calcium oxide which is 0.3 times the mass of sodium ethoxide, react for 1.5 h, transfer to a drying oven at 75°C for drying to obtain oxazolidine tetracarboxylic acid; S4. Mix compound triazine - methyl oxazole, oxazolidine tetracarboxylic acid and additive ferric sulfate at a mass ratio of 55:15:5, heat up to 50°C and stir evenly to obtain the triazine - type desulfurizer. Example

[0018] The preparation method of the triazine - type desulfurizer in this example is as follows: S1. Heat up formaldehyde to 45°C, add sulfamethoxazole with the same mass, dropwise add sulfuric acid with a mass fraction of 5% which is 0.4 times the mass of formaldehyde at a rate of 3 ml / min, keep the temperature for reaction for 10 h, and perform vacuum distillation to obtain triazine - methyl oxazole: S2. Mix triazine - methyl oxazole and fatty alcohol polyoxyethylene ether at a mass ratio of 20:3, heat up to 60°C and stir at 400 rpm for 10 min to obtain compound triazine - methyl oxazole: S3. Mix toluene and diethanolamine at a mass ratio of 2:1.04, stir evenly, then heat up to 42 °C, and dropwise add acetone which is 1.3 times the mass of diethanolamine at a rate of 3 ml / min. React for 2 h, then heat up to 62 °C and reflux for 5 h. After cooling to room temperature, perform vacuum fractional distillation and collect the fraction at 65 °C to obtain hydroxyethyl oxazolidine; Under a nitrogen atmosphere, mix sodium and absolute ethanol at a mass ratio of 1.2:20, stir to dissolve, then add diethyl diethylmalonate which is 10 times the mass of sodium. After reacting for 6 h, dropwise add 1,3-bromopropane at a rate of 3 ml / min, heat up to 70 °C, and reflux for 16 h. Perform vacuum distillation, then add sulfuric acid with a mass fraction of 5% which is 0.6 times the mass of sodium, let it stand for layering, extract with ethyl acetate, dry with anhydrous magnesium sulfate, and perform column chromatography separation with petroleum ether and ethyl acetate at a volume ratio of 20:1 after vacuum distillation to obtain tetraethyl endo-tetracarboxylate; Under a nitrogen atmosphere, mix sodium ethoxide, tetraethyl endo-tetracarboxylate and hydroxyethyl oxazolidine at a mass ratio of 3:8:22, stir evenly, then heat up to 115 °C and reflux for 4 h. Then reduce the pressure to 10 kPa and continue to react for 4 h. Heat up to 130 °C, perform vacuum distillation, add p-toluenesulfonic acid which is 5 times the mass of sodium ethoxide and methyl ethyl ketone which is 0.04 times the mass of sodium ethoxide, stir evenly, then add calcium oxide which is 0.25 times the mass of sodium ethoxide, react for 2 h, transfer to a drying oven at 80 °C for drying to obtain oxazolidine tetracarboxylic acid. S4. Mix compound triazine methyloxazole, oxazolidine tetracarboxylic acid and additive ferric acetate at a mass ratio of 60:20:8, heat up to 55 °C, and stir evenly to obtain the triazine desulfurizer.

[0019] Comparative Example 1 The preparation method of Comparative Example 1 is the same as that of Example 2. The difference between this triazine desulfurizer and Example 2 is that the compound triazine methyloxazole is prepared by reacting sulfamethoxazole with paraformaldehyde.

[0020] Comparative Example 2 The preparation method of Comparative Example 2 is the same as that of Example 2. The difference between this triazine desulfurizer and Example 2 is that the compound triazine methyloxazole is prepared by reacting ethanolamine with paraformaldehyde and then mixing with fatty alcohol polyoxyethylene ether.

[0021] Comparative Example 3 The preparation method of Comparative Example 3 is the same as that of Example 2. The difference between this triazine desulfurizer and Example 2 is that it includes compound triazine methyloxazole, hydroxyethyl oxazolidine and additive ferric sulfate.

[0022] Comparative Example 4 The preparation method of Comparative Example 4 is the same as that of Example 2. The difference between this triazine desulfurizer and Example 2 is that it only includes compound triazine methyloxazole and additive ferric sulfate.

[0023] Effect Example The concentration of hydrogen sulfide in the crude oil is 5240 ppm. Table 1 below shows the performance test results of the triazine desulfurizers prepared in the examples and comparative examples; Table 1 From the comparison of the performance data in Table 1, it can be seen that the triazine desulfurizer prepared by the present invention not only has excellent desulfurization rate, but also has a wider applicable temperature range; From the comparison of the experimental data of Example 1, Example 2, Example 3 and Comparative Example 1, Comparative Example 2, it can be found that sulfamethoxazole and paraformaldehyde undergo aminoaldehyde condensation to form triazine sulfamethoxazole with a benzene ring side chain, which increases the compatibility with the crude oil and makes full contact with the sulfur-containing substances in the crude oil, thereby improving the desulfurization rate. It can also increase the reaction temperature of the triazine desulfurizer and has a higher applicable temperature. Then, it is mixed with the surfactant fatty alcohol polyoxyethylene ether, thereby reducing the surface tension of the system and further increasing the compatibility between the triazine desulfurizer and the crude oil, and the desulfurization rate is further improved.

[0024] From the comparison of the experimental data of Example 1, Example 2, Example 3 and Comparative Example 3, Comparative Example 4, it can be found that oxazolidine with a hydroxyethyl group is prepared by reacting diethanolamine and acetone, and then reacting with tetraethyl terminal tetracarboxylate formed by the reaction of diethyl diethylmalonate and 1,3-bromopropane to prepare symmetric tetracarboxylic acid oxazolidine. The higher functionality of tetracarboxylic acid oxazolidine further enhances the compatibility with the crude oil and improves the desulfurization rate.

[0025] Obviously, the above-mentioned embodiments are merely examples for clearly illustrating the embodiments of the present invention, and are not intended to limit the embodiments of the present invention. For those of ordinary skill in the art, other different forms of changes or modifications can be made on the basis of the above description. It is not necessary and impossible to enumerate all the embodiments here. And these obvious changes or modifications derived from the spirit of the present invention are still within the protection scope of the present invention.

Claims

1. A triazine-based desulfurizer, characterized in that, It includes compound triazine methoxazole, oxazolidine tetracarboxylic acid and an additive; the compound triazine methoxazole is prepared by reacting sulfamethoxazole with paraformaldehyde and then mixing with fatty alcohol polyoxyethylene ether.

2. The triazine-based desulfurizer according to claim 1, wherein The oxazolidine tetracarboxylic acid is prepared by reacting diethyl diethylmalonate with 1,3-bromopropane and then reacting with hydroxyethyl oxazolidine.

3. The triazine desulfurizer according to claim 2, wherein, The hydroxyethyl oxazolidine is prepared by reacting diethanolamine and acetone.

4. The triazine desulfurizer according to claim 1, characterized in that, The additive is one of ferric sulfate or ferric acetate.

5. The preparation method of a triazine-based desulfurizer according to claim 1, characterized in that, It includes the following specific steps: S1. Heat formaldehyde to 35 - 45°C, add an equal mass of sulfamethoxazole, dropwise add sulfuric acid with a mass fraction of 3 - 5% and 0.2 - 0.4 times the mass of formaldehyde at a rate of 1 - 3 ml / min, keep the temperature for reaction for 8 - 10 h, and carry out vacuum distillation to obtain triazine methoxazole: S2. Mix triazine methoxazole and fatty alcohol polyoxyethylene ether according to a mass ratio of 20:1 - 3, heat to 50 - 60°C, stir at 200 - 400 rpm for 8 - 10 min to obtain compound triazine methoxazole: S3. Under a nitrogen atmosphere, mix sodium ethoxide, tetraethyl endo-tetracarboxylate and hydroxyethyl oxazolidine according to a mass ratio of 3:8:20 - 22, stir evenly, heat to 105 - 115°C, reflux for 3 - 4 h, reduce the pressure to 8 - 10 kPa, continue the reaction for 3 - 4 h, heat to 120 - 130°C, carry out vacuum distillation, then add p-toluenesulfonic acid with 3 - 5 times the mass of sodium ethoxide and methyl ethyl ketone with 0.02 - 0.04 times the mass of sodium ethoxide, stir evenly, then add calcium oxide with 0.15 - 0.25 times the mass of sodium ethoxide, react for 1 - 2 h, transfer to a drying oven at 70 - 80°C for drying to obtain oxazolidine tetracarboxylic acid; S4. Mix compound triazine methoxazole, oxazolidine tetracarboxylic acid and the additive, heat to 45 - 55°C, stir evenly to obtain a triazine-based desulfurizer.

6. The preparation method of a triazine-based desulfurizer according to claim 5, characterized in that, In the above step S3, the preparation method of hydroxyethyl oxazolidine is as follows: Mix toluene and diethanolamine according to a mass ratio of 2:1 - 1.04, stir evenly, heat to 40 - 42°C, dropwise add acetone with 1.1 - 1.3 times the mass of diethanolamine at a rate of 1 - 3 ml / min, react for 1 - 2 h, heat to 60 - 62°C, reflux for 3 - 5 h, cool to room temperature and then carry out vacuum fractionation, collect the fraction at 65°C to obtain hydroxyethyl oxazolidine.

7. The preparation method of a triazine-based desulfurizer according to claim 5, characterized in that, In the above step S3, the preparation method of tetraethyl endo-tetracarboxylate is as follows: Under a nitrogen atmosphere, mix sodium and absolute ethanol according to a mass ratio of 1 - 1.2:20, stir and dissolve, then add diethyl diethylmalonate with 8 - 10 times the mass of sodium, react for 4 - 6 h, dropwise add 1,3-bromopropane at a rate of 1 - 3 ml / min, heat to 60 - 70°C, reflux for 14 - 16 h, carry out vacuum distillation, then add sulfuric acid with a mass fraction of 3 - 5% and 0.2 - 0.6 times the mass of sodium, let it stand for stratification, extract with ethyl acetate, dry with anhydrous magnesium sulfate, carry out vacuum distillation, and then separate by column chromatography of petroleum ether and ethyl acetate with a volume ratio of 20:1 to obtain tetraethyl endo-tetracarboxylate.

8. The preparation method of a triazine-based desulfurizer according to claim 5, characterized in that, In the above step S4, the mass ratio of compound triazine methoxazole, oxazolidine tetracarboxylic acid and the additive is 50 - 60:10 - 20:3 - 8.

9. Use of a triazine desulfurizer according to claim 1, characterized in that, The triazine desulfurizer is applied to desulfurize crude oil.