阅读说明：本技术 一种用于燃料油脱硫的添加剂 (Additive for fuel oil desulfurization ) 是由 熊长祥 程秀丽 于 2021-06-30 设计创作，主要内容包括：本申请公开了一种用于燃料油脱硫的添加剂,按重量份数计,制备所述添加剂所需的原料包括以下组分：表面活性剂30-60份、促燃剂10-30份、稳定剂5-20份、脱附剂20-50份和纳米微粒3-10份；所述脱附剂由溶剂和酰胺类化合物组成。该添加剂脱硫效果好,并且提高了燃烧效率,还能起到降粘和降凝的作用,解决了现有添加剂功能单一,脱硫效果差的问题。(The application discloses an additive for fuel oil desulfurization, which comprises the following raw materials in parts by weight: 30-60 parts of surfactant, 10-30 parts of combustion promoter, 5-20 parts of stabilizer, 20-50 parts of desorbent and 3-10 parts of nano particles; the desorption agent consists of a solvent and an amide compound. The additive has good desulfurization effect, improves the combustion efficiency, can also play the roles of viscosity reduction and pour point depression, and solves the problems of single function and poor desulfurization effect of the existing additive.)

1. The additive for desulfurizing the fuel oil is characterized in that raw materials required for preparing the additive comprise the following components in parts by weight: 30-60 parts of surfactant, 10-30 parts of combustion promoter, 5-20 parts of stabilizer, 20-50 parts of desorbent and 3-10 parts of nano particles;

the desorption agent consists of a solvent and an amide compound.

2. The additive for desulfurizing fuel oil according to claim 1, wherein said surfactant is a cationic surfactant, and said cationic surfactant is at least one or more of dodecyldimethyl phenyl phosphonium bromide, dodecyltrimethyl ammonium bromide and hexadecyltrimethyl ammonium chloride.

3. The additive for desulfurizing fuel oil according to claim 2, wherein said cationic surfactant is dodecyldimethylphenylphosphine bromide.

4. The additive for desulfurizing fuel oil according to claim 1, wherein said solvent is hexamethylphosphoramide, said amide compound is N-methyldiethylamide, and the mass ratio of hexamethylphosphoramide to N-methyldiethylamide is 2 (0.5-1).

5. The additive for desulfurizing fuel oil according to claim 4, wherein said combustion accelerator is composed of isooctyl nitrate and 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate, and the mass ratio of isooctyl nitrate to 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate is 3 (0.5-2).

6. Additive for desulfurization of fuel oil according to claim 5, characterized in that said stabilizer is sodium salt of pentadecane sulfonic acid.

7. The additive for desulfurizing fuel oil according to claim 6, wherein said nanoparticles are nano silver oxide having a particle size of 20 to 80 nm.

8. A method for preparing the additive for desulfurizing fuel oil according to any one of claims 1 to 7, comprising the steps of:

1) mixing a surfactant, a combustion promoter, a stabilizer and 50% of desorbent by mass, adding into a reaction kettle, uniformly stirring at 40-80 ℃ for 20-60 minutes, and cooling to room temperature;

2) adding the rest 50% of desorption agent and nano particles into a reaction kettle, heating to 50-80 ℃, and uniformly stirring for 30-60 minutes to obtain the catalyst.

9. The method for preparing the additive for desulfurization of fuel oil according to claim 8, wherein the temperature in step 1) is 50 ℃ and the temperature in step 2) is 65 ℃.

10. The method as claimed in claim 9, wherein the stirring rate in step 1) is 200-400r/min, and the stirring rate in step 2) is 500-700 r/min.

Technical Field

The application relates to an additive for fuel oil desulfurization, belonging to the field of fuel oil additives.

Background

Ships are the main mode of global trade transportation, and along with the rapid development of the world economy, the pollution caused by the ships is more and more serious, and the proportion of the pollution caused by the ships is up to 45% taking petroleum pollutants as an example. The marine fuel oil is generally heavy oil, has large molecular weight and high viscosity, and gradually becomes a great trend of low vulcanization and light weight under the large background that the environmental protection requirement is increasingly strict.

The existing fuel oil additive mainly aims at improving the combustion condition of fuel oil, and comprises an antiknock agent, an antioxidant, a metal deactivator, an antistatic agent, an antiwear and antirust agent, a flow improver and the like, and phosphate or a phosphate derivative is a main component of the existing fuel oil additive, so that the existing fuel oil additive can play roles in resisting wear and rust and resisting oxidation and ageing. However, the existing fuel oil additive has little desulfurization effect, even if the fuel oil additive has desulfurization effect, the desulfurization effect on Benzothiophene (BT) sulfides is poor, and thiophenes account for 70-80% of the total sulfur of the fuel oil.

Disclosure of Invention

In order to solve the problems, the additive for desulfurizing the fuel oil is provided, has good desulfurization effect, improves the combustion efficiency, can also play the roles of reducing viscosity and pour point, and solves the problems of single function and poor desulfurization effect of the existing additive.

According to one aspect of the application, an additive for desulfurizing fuel oil is provided, and raw materials required for preparing the additive comprise the following components in parts by weight: 30-60 parts of surfactant, 10-30 parts of combustion promoter, 5-20 parts of stabilizer, 20-50 parts of desorbent and 3-10 parts of nano particles; the desorption agent consists of a solvent and an amide compound.

Optionally, the surfactant is a cationic surfactant that is at least one or more of dodecyldimethyl phenyl phosphonium bromide, dodecyltrimethyl ammonium bromide, and hexadecyltrimethyl ammonium chloride.

Optionally, the cationic surfactant is dodecyl dimethyl phenyl phosphonium bromide.

Optionally, the solvent is hexamethylphosphoramide, the amide compound is N-methyldiethylamide, and the mass ratio of the hexamethylphosphoramide to the N-methyldiethylamide is 2 (0.5-1).

Optionally, the combustion accelerator consists of isooctyl nitrate and 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate, and the mass ratio of the isooctyl nitrate to the 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate is 3 (0.5-2).

Optionally, the stabilizer is sodium pentadecanesulfonate.

Optionally, the nanoparticles are nano silver oxide with a particle size of 20-80 nm.

According to still another aspect of the present application, there is provided a method for preparing the above additive for desulfurization of fuel oil, comprising the steps of:

1) mixing a surfactant, a combustion promoter, a stabilizer and 50% of desorbent by mass, adding into a reaction kettle, uniformly stirring at 40-80 ℃ for 20-60 minutes, and cooling to room temperature;

2) adding the rest 50% of desorption agent and nano particles into a reaction kettle, heating to 50-80 ℃, and uniformly stirring for 30-60 minutes to obtain the catalyst.

Alternatively, the temperature in step 1) is 50 ℃ and the temperature in step 2) is 65 ℃.

Optionally, the stirring speed in the step 1) is 200-400r/min, and the stirring speed in the step 2) is 500-700 r/min.

In the present application, "room temperature" means 25 ℃.

Benefits of the present application include, but are not limited to:

1. according to the additive for desulfurizing the fuel oil, the stabilizer sodium pentadecanesulfonate is added, so that the stability of the fuel oil during storage can be improved, a certain anti-coagulation effect is achieved, and the whole additive system can be kept uniform and stable.

2. According to the additive for desulfurizing the fuel oil, the cationic surfactant is adopted, so that the surface tension of the fuel oil is reduced, and the viscosity reduction effect and a certain pour point depression effect are achieved.

3. According to the additive for desulfurizing the fuel oil, the desorption agent is formed by combining hexamethylphosphoramide and N-methyldiethanamide, so that Benzothiophene (BT) sulfides can be obviously removed, and a good desulfurization effect is achieved.

4. According to the additive for desulfurizing the fuel oil, the combustion accelerator is composed of isooctyl nitrate and 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate, so that the combustion proportion of components with large molecular weight in the heavy oil can be increased, the combustion lag phase of the heavy oil is shortened, and the combustion efficiency is improved.

5. According to the additive for desulfurizing the fuel oil, the nano silver oxide is added, the dispersibility of an additive system is improved, a plurality of reaction active centers can be generated, micro explosion is generated during combustion, the atomization effect is improved, and a good combustion oxidation catalysis effect is achieved.

6. According to the additive for desulfurizing the fuel oil, the desulfurization effect is good, the combustion efficiency is improved, the effects of reducing viscosity and pour point can be achieved, and the problems that the existing additive is single in function and poor in desulfurization effect are solved.

7. According to the preparation method of the additive for desulfurizing the fuel oil, the method is simple in process steps, easy to prepare and convenient for realizing industrial production.

Detailed Description

The present application will be described in detail with reference to examples, but the present application is not limited to these examples.

Unless otherwise specified, the raw materials and catalysts in the examples of the present application were all purchased commercially.

EXAMPLE 1 preparation of additive No. 1

1) Mixing 300g of dodecyl dimethyl phenyl phosphorus bromide, 100g of a combustion promoter (the mass ratio of isooctyl nitrate to 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate is 3:0.5), 50g of pentadecane sulfonic acid sodium salt and 100g of a desorption agent (the mass ratio of hexamethylphosphoramide to N-methyldiethanamide is 2:0.5), adding into a reaction kettle, uniformly stirring at 50 ℃ for 20 minutes at a constant speed of 200r/min, and cooling to room temperature;

2) then 100g of desorption agent (the mass ratio of hexamethylphosphoramide to N-methyldiethanamide is 2:0.5) and 30g of nano silver oxide (the particle size is 20nm) are added into the reaction kettle, the temperature is raised to 65 ℃, the mixture is stirred at a constant speed for 30 minutes, and the stirring speed is 500r/min, thus obtaining the additive 1 #.

EXAMPLE 2 preparation of additive No. 2

1) Mixing 450g of dodecyl dimethyl phenyl phosphorus bromide, 200g of a combustion promoter (the mass ratio of isooctyl nitrate to 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate is 3:1), 100g of pentadecane sulfonic acid sodium salt and 150g of a desorption agent (the mass ratio of hexamethylphosphoramide to N-methyldiethanamide is 2:0.8), adding into a reaction kettle, uniformly stirring at 50 ℃ for 40 minutes at a constant speed of 300r/min, and cooling to room temperature;

2) adding 150g of desorbent (the mass ratio of hexamethylphosphoramide to N-methyldiethanamide is 2:0.8) and 50g of nano silver oxide (the particle size is 40nm) into the reaction kettle, heating to 65 ℃, uniformly stirring for 45 minutes at a constant speed of 600r/min, and obtaining the additive 2 #.

EXAMPLE 3 preparation of additive # 3

1) Mixing 600g of dodecyl dimethyl phenyl phosphorus bromide, 300g of a combustion promoter (the mass ratio of isooctyl nitrate to 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate is 3:2), 200g of pentadecane sulfonic acid sodium salt and 250g of a desorption agent (the mass ratio of hexamethylphosphoramide to N-methyl-diethylamide is 2:1) and adding into a reaction kettle, uniformly stirring at 50 ℃ for 60 minutes at a constant speed, wherein the stirring speed is 400r/min, and cooling to room temperature;

2) adding 250g of desorbent (the mass ratio of hexamethylphosphoramide to N-methyldiethanamide is 2:0.5) and 100g of nano silver oxide (the particle size is 80nm) into the reaction kettle, heating to 65 ℃, and uniformly stirring for 60 minutes at the stirring speed of 700r/min to obtain the additive 3 #.

Comparative example 1 preparation of comparative additive D1#

The 300g desorbent used in the preparation of comparative additive D1# was a mixture of alumina, zinc oxide and activated carbon, wherein the mass ratio of alumina, zinc oxide and activated carbon was 3:2:0.8, and the reaction conditions of the other steps and the raw material amounts were the same as those of additive 2# prepared in example 2.

Comparative example 2 preparation of comparative additive D2#

The mass ratio of hexamethylphosphoramide to N-methyldiethanamide in the desorbent in the preparation of comparative additive D2# was 4:1, and the reaction conditions of other steps, the amounts of raw materials, and the like were the same as those in the preparation of additive 2# in example 2.

Comparative example 3 preparation of comparative additive D3#

The flame retardant used in the preparation of comparative additive D3# was isooctyl nitrate, and the reaction conditions of the other steps and the raw material amounts were the same as those of additive 2# prepared in example 2.

Comparative example 4 preparation of comparative additive D4#

The comparative additive D4# was prepared without adding nano-silver oxide, and the reaction conditions of other steps, raw material usage, etc. were the same as those for the additive 2# prepared in example 2.

Comparative example 5 preparation of comparative additive D5#

The surfactant used in the preparation of comparative additive D5# was perfluoroalkyl acyl quaternary ammonium salt type cationic fluorocarbon surfactant [ C₇H₁₅CONH(CH₂)₃N⁺(CH₃)₃I^-]The reaction conditions of other steps and the amounts of the raw materials were the same as those for preparing additive No. 2 in example 2.

Example 4 Performance testing

1. Desulfurization Effect test

The test method comprises the following steps: the test is carried out by adopting the GB/T380 standard, 180# heavy oil is selected, the sulfur content is 2.5%, the addition amount of various additives is 1% of the mass of the average heavy oil, 8 kinds of heavy oil are prepared, and the test results are shown in Table 1.

TABLE 1

The result shows that the additive 1# -3# prepared by the embodiment of the application has obvious desulfurization effect, and the sulfur content in the heavy oil can be reduced to below 1%; the desorption agent consisting of alumina, zinc oxide and activated carbon is used in the comparative additive D1#, the mass ratio of hexamethylphosphoramide to N-methyldiethylamide in the comparative additive D2# is 4:1, and the desorption agent is out of the range defined by the application, finally the sulfur content of the heavy oil is reduced to 2.1% by the comparative additive D1#, the sulfur content of the heavy oil is reduced to 1.9% by the comparative additive D2#, and the desulfurization effect is obviously lower than that of the additive 1# -3 #; the desulfurization effect of comparative additives D3# -D5# was comparable to additives 1# -3 #.

2. Viscosity and set point test

The detection method comprises the following steps: detecting kinematic viscosity according to the standard of GB/T11137; testing the condensation point according to the method of GB/T510;

selecting 180# heavy oil with the kinematic viscosity of 180mm at 50 DEG C²The condensation point is 24 ℃, the addition amount of each additive is 1 percent of the mass of the average heavy oil, 8 heavy oils are prepared, and the test results are shown in table 2.

TABLE 2

The result shows that the additive 1# to 3# prepared by the embodiment of the application has obvious pour point depressing and viscosity reducing effects, and compared with the additive D4# without using nano particles, the final dispersibility is poor, and the pour point depressing and viscosity reducing effects are not obvious; as comparative additive D5#, used was a perfluoroalkyl acyl quaternary ammonium salt type cationic fluorocarbon surfactant [ C₇H₁₅CONH(CH₂)₃N⁺(CH₃)₃I^-]Finally, the viscosity reduction and pour point depression effects are poor; the pour point and viscosity reducing effects of the comparative additives D1# -D3# are equivalent to those of additives 1# -3 #.

3. Combustion efficiency test

The test method comprises the following steps: the test is carried out according to GB/T384, 180# heavy oil is selected, the addition amount of various additives is 1 percent of the mass of the average heavy oil, 8 heavy oils are prepared, 10g of 8 heavy oils and 10g of common heavy oil are respectively taken by adopting an oxygen bomb heat value comparison method, the volume of the oxygen bomb is 2.5L, the oxygen pressure is 1MPa, and the results are shown in Table 3.

TABLE 3

The result shows that the additive 1# -3# prepared by the embodiment of the application has a remarkable effect of improving the combustion efficiency, and compared with the additive D3# in which single-component isooctyl nitrate is used, the combustion efficiency is lower; compared with the additive D4#, the nano particles are not used, the dispersibility is poor, and the final combustion efficiency is lower; the combustion efficiency improving effects of the comparative additives D1# -D2# and D5# are equivalent to those of the additives 1# -3 #.

The above description is only an example of the present application, and the protection scope of the present application is not limited by these specific examples, but is defined by the claims of the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the technical idea and principle of the present application should be included in the protection scope of the present application.