阅读说明：本技术 一种燃料油脱硫净化方法 (Fuel oil desulfurization purification method ) 是由 车春玲 王本山 于 2021-08-10 设计创作，主要内容包括：本申请公开了一种燃料油脱硫净化方法,属于石油化工领域,其将燃料油与吡咯烷类离子液体和降粘分散剂混合均匀,再加入氧化脱附剂,反应结束后将吡咯烷类离子液体分离,得到清洁燃料油；所述吡咯烷类离子液体与所述氧化脱附剂的质量比为(5-10)：1；所述氧化脱附剂为石墨烯负载纳米金属氧化物。该方法不仅能够深入脱除燃料油中的硫化物,还能够降低燃料油的粘度,且反应条件温和,能耗成本低。(The application discloses a fuel oil desulfurization purification method, which belongs to the field of petrochemical industry, and comprises the steps of uniformly mixing fuel oil, pyrrolidine ionic liquid and a viscosity reduction dispersant, adding an oxidation desorbent, and separating the pyrrolidine ionic liquid after the reaction is finished to obtain clean fuel oil; the mass ratio of the pyrrolidine ionic liquid to the oxidation desorbent is (5-10): 1; the oxidation desorbent is graphene loaded nanometer metal oxide. The method can not only deeply remove sulfides in the fuel oil, but also reduce the viscosity of the fuel oil, and has mild reaction conditions and low energy consumption and cost.)

1. A fuel oil desulfurization purification method is characterized in that fuel oil is uniformly mixed with pyrrolidine ionic liquid and viscosity reduction dispersant, then oxidation desorbent is added, and after the reaction is finished, the pyrrolidine ionic liquid is separated to obtain clean fuel oil;

the mass ratio of the pyrrolidine ionic liquid to the oxidation desorbent is (5-10): 1; the oxidation desorbent is graphene loaded nanometer metal oxide.

2. The fuel oil desulfurization purification method according to claim 1, wherein the mass ratio of the viscosity-reducing dispersant to the oxidative desorbent is (1-4): 1.

3. the method for desulfurizing and purifying fuel oil according to claim 2, wherein the pyrrolidine ionic liquid is an N-methyl-N-ethylpyrrolidine aluminum chloride ionic liquid generated by the reaction of N-methyl-N-ethylpyrrolidine chloride salt and aluminum chloride.

4. The method for desulfurizing and purifying fuel oil according to claim 3, wherein the N-methyl-N-ethyl pyrrolidine aluminum chloride ionic liquid is prepared by mixing N-methyl-N-ethyl pyrrolidine with concentrated hydrochloric acid, heating to 60-80 ℃, reacting for 6-8h, adding aluminum chloride solution, heating to 80-100 ℃, and reacting for 3-6 h.

5. The fuel oil desulfurization purification method according to claim 4, characterized in that the molar ratio of N-methyl-N-ethylpyrrolidine to concentrated hydrochloric acid is (0.5-0.8):1, and the molar ratio of N-methyl-N-ethylpyrrolidine to the aluminum chloride solution is (0.5-1): 1.

6. the fuel oil desulfurization purification method according to claim 5, wherein the graphene-supported nano metal oxide is graphene-supported nano magnesium oxide.

7. The fuel oil desulfurization purification method according to claim 6, wherein the graphene-supported nano metal is prepared by using graphene as a carrier and nano magnesium oxide as a precursor, ultrasonically dispersing the graphene-supported nano metal in water at 40-80 ℃ for 2-4h, and drying the dispersion product to obtain the graphene-supported nano magnesium oxide.

8. The fuel oil desulfurization purification method according to claim 7, wherein the viscosity-reducing dispersant is at least one or more of a maleic anhydride copolymer and a sulfonate.

9. The method for desulfurizing and purifying fuel oil according to claim 8, wherein the viscosity-reducing dispersant is composed of a maleic anhydride copolymer and a sulfonate, and the mass ratio of the viscosity-reducing dispersant to the sulfonate is 20: (2-8).

10. The fuel oil desulfurization purification method according to claim 9, wherein the maleic anhydride copolymer is a sulfonated styrene-maleic anhydride copolymer, and the sulfonate is a secondary sodium alkyl sulfonate.

Technical Field

The application relates to a fuel oil desulfurization purification method, belonging to the technical field of petrochemical industry.

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 fuel oil is also called heavy oil, is mainly prepared from cracked residual oil and straight-run residual oil of petroleum, is characterized by large viscosity, containing non-hydrocarbon compounds, colloid and asphaltene, high sulfur content, and great difference with the traditional vehicle gasoline and diesel oil, is generally used as ship fuel, and has the great trend of low vulcanization and light weight of the fuel oil under the large background of increasingly strict environmental protection requirements.

The existing fuel oil hydrogenation device widely applied in industrialization has the problems of harsh reaction conditions and high energy consumption, and due to the stereoscopic effect of alkyl substituent groups, the efficiency of the hydrogenation desulfurization device for removing thiophene and thiophene derivatives is very limited. The non-hydrodesulfurization technology mainly comprises oxidative desulfurization, adsorption desulfurization, extraction desulfurization, biological desulfurization and active metal desulfurization, can perform fuel oil desulfurization reaction under mild conditions, and has good removal effect on thiophene sulfides which are difficult to remove by hydrodesulfurization.

Chinese patent CN111040804A discloses a desulfurization method for catalytic oxidation of fuel oil by using ionic liquid, which aims at desulfurization of vehicle gasoline and diesel oil, and has short reaction time and final desulfurization rate reaching 78%. The viscosity of the marine heavy oil is high, the sulfur content is high, the common desulfurizer is difficult to be uniformly dispersed in the heavy oil, and the effective desulfurization can not be realized by the desulfurization method.

Disclosure of Invention

In order to solve the problems, the method for desulfurizing and purifying the fuel oil is provided, the method not only can deeply remove sulfides in the fuel oil, but also can reduce the viscosity of the fuel oil, and has mild reaction conditions and low energy consumption cost.

According to another aspect of the application, a fuel oil desulfurization purification method is provided, wherein fuel oil is uniformly mixed with pyrrolidine ionic liquid and a viscosity-reducing dispersant, then an oxidation desorbent is added, and after the reaction is finished, the pyrrolidine ionic liquid is separated to obtain clean fuel oil;

the mass ratio of the pyrrolidine ionic liquid to the oxidation desorbent is (5-10): 1; the oxidation desorbent is graphene loaded nanometer metal oxide.

Preferably, the fuel oil, the pyrrolidine ionic liquid and the viscosity-reducing dispersant are uniformly mixed, stirred for 2-5 hours at the temperature of 60-90 ℃, then the oxidation desorbent is added, stirred for 1-3 hours at the temperature of 40-70 ℃, standing and layering are carried out after the reaction is finished, and the pyrrolidine ionic liquid is separated to obtain the clean fuel oil.

Optionally, the mass ratio of the viscosity-reducing dispersant to the oxidative desorbent is (1-4): 1.

optionally, the pyrrolidine ionic liquid is an N-methyl-N-ethylpyrrolidine aluminum chloride ionic liquid generated by reacting an N-methyl-N-ethylpyrrolidine chloride salt with aluminum chloride.

Optionally, the preparation method of the N-methyl-N-ethylpyrrolidine aluminum chloride ionic liquid comprises the steps of mixing N-methyl-N-ethylpyrrolidine and concentrated hydrochloric acid, heating to 60-80 ℃, reacting for 6-8 hours, adding an aluminum chloride solution, heating to 80-100 ℃, and reacting for 3-6 hours to obtain the N-methyl-N-ethylpyrrolidine aluminum chloride ionic liquid.

Alternatively, the molar ratio of the N-methyl-N-ethylpyrrolidine to the concentrated hydrochloric acid is (0.5-0.8):1, and the molar ratio of the N-methyl-N-ethylpyrrolidine to the aluminum chloride solution is (0.5-1): 1.

optionally, the graphene-supported nano metal oxide is graphene-supported nano magnesium oxide.

Optionally, the preparation method of the graphene-supported nano metal comprises the steps of taking graphene as a carrier, taking nano magnesium oxide as a precursor, performing ultrasonic dispersion for 2-4 hours in water at 40-80 ℃, and drying to obtain the graphene-supported nano magnesium oxide.

Optionally, the viscosity reducing dispersant is at least one or more of a maleic anhydride copolymer and a sulfonate.

Optionally, the viscosity-reducing dispersant consists of a maleic anhydride copolymer and a sulfonate, and the mass ratio of the maleic anhydride copolymer to the sulfonate is 20: (2-8).

Optionally, the maleic anhydride copolymer is a sulfonated styrene-maleic anhydride copolymer and the sulfonate is a secondary sodium alkyl sulfonate.

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

1. according to the fuel oil desulfurization purification method, the sulfide in the fuel oil can be deeply removed, the viscosity of the fuel oil can be reduced, the combustion efficiency of the fuel oil can be improved, the reaction condition is mild, and the energy consumption cost is low.

2. According to the fuel oil desulfurization purification method, the N-methyl-N-ethyl pyrrolidine aluminum chloride ionic liquid is used, has good affinity with sulfides in the fuel oil, can be quickly combined with Benzothiophene (BT) sulfides, and is matched with the viscosity-reducing dispersing agent, wherein the surface tension of the fuel oil can be reduced by the secondary alkyl sodium sulfonate, the mobility of the N-methyl-N-ethyl pyrrolidine aluminum chloride ionic liquid in the fuel oil is improved, the contact area of the N-methyl-N-ethyl pyrrolidine aluminum chloride ionic liquid and the fuel oil is increased, and the extraction effect is enhanced.

3. According to the fuel oil desulfurization purification method, the graphene loaded nano magnesium oxide is used as the oxidation desorbent, the graphene has a good adsorption effect due to a layered structure and a large surface area, and in addition, magnesium ions on the surface of the graphene can form chemical bonds with sulfur through pi complexation with sulfides in the fuel oil, so that the sulfides in the fuel oil can be deeply desorbed, physical adsorption and chemical adsorption can be simultaneously realized, and the desulfurization rate is high.

4. According to the fuel oil desulfurization purification method, viscosity in the fuel oil is reduced and fluidity is improved by adding the viscosity reduction dispersant, the graphene-loaded nano magnesium oxide is added, and the mass ratio of the graphene-loaded nano magnesium oxide to the N-methyl-N-ethyl pyrrolidine aluminum chloride ionic liquid is limited, so that the graphene-loaded nano magnesium oxide and the sulfonated styrene-maleic anhydride copolymer can form mutually attached adsorption 'particles', the sulfonated styrene-maleic anhydride copolymer can further improve the dispersibility of the graphene-loaded nano magnesium oxide and the N-methyl-N-ethyl pyrrolidine aluminum chloride ionic liquid in the fuel oil, the desulfurization time is shortened, and the fuel oil desulfurization effect is excellent.

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 stated, the raw materials and catalysts in the examples of this application were purchased commercially, wherein the ultrasonic device for preparing the oxidative desorbent in this application was a KQ-200VDE desktop dual-frequency numerical control ultrasonic cleaner.

Example 1 clean Fuel oil 1#

Preparation of N-methyl-N-ethyl pyrrolidine aluminium chloride ionic liquid

Mixing 0.7mol of N-methyl-N-ethyl pyrrolidine with 1mol of concentrated hydrochloric acid, heating to 70 ℃, reacting for 7 hours, adding 1mol of aluminum chloride solution, heating to 90 ℃, and reacting for 5 hours to obtain the compound.

2. Preparation of graphene loaded nano magnesium oxide

Adding 10g of graphene oxide and 50g of nano magnesium oxide into water, performing ultrasonic dispersion for 3 hours at 60 ℃, and drying to obtain the graphene-loaded nano magnesium oxide.

3. Uniformly mixing 100g of 180# heavy oil, 7g N-methyl-N-ethyl pyrrolidine aluminum chloride ionic liquid and 2g of viscosity reduction dispersant (wherein the mass ratio of sulfonated styrene-maleic anhydride copolymer to secondary alkyl sodium sulfonate is 20: 4), stirring for 3h at 70 ℃, adding 1g of graphene-loaded nano magnesium oxide, stirring for 2h at 50 ℃, standing for layering after the reaction is finished, and separating the ionic liquid to obtain the clean fuel oil 1 #.

Example 2 clean Fuel oil 2#

Preparation of N-methyl-N-ethyl pyrrolidine aluminium chloride ionic liquid

Mixing 0.5mol of N-methyl-N-ethyl pyrrolidine with 1mol of concentrated hydrochloric acid, heating to 60 ℃, reacting for 6h, adding 1mol of aluminum chloride solution, heating to 80 ℃, and reacting for 3h to obtain the compound.

2. Preparation of graphene loaded nano magnesium oxide

And adding 10g of graphene oxide and 50g of magnesium oxide into water, performing ultrasonic dispersion for 2 hours at 40 ℃, and drying to obtain the graphene-loaded nano magnesium oxide.

3. Uniformly mixing 100g of 180# heavy oil, 5g N-methyl-N-ethyl pyrrolidine aluminum chloride ionic liquid and 1g of viscosity reduction dispersant (wherein the mass ratio of the sulfonated styrene-maleic anhydride copolymer to the secondary alkyl sodium sulfonate is 20: 2), stirring at 60 ℃ for 2h, adding 1g of graphene-loaded nano magnesium oxide, stirring at 40 ℃ for 1h, standing for layering after the reaction is finished, and separating the ionic liquid to obtain the clean fuel oil 2 #.

Example 3 clean Fuel oil 3#

Preparation of N-methyl-N-ethyl pyrrolidine aluminium chloride ionic liquid

Mixing 0.8mol of N-methyl-N-ethyl pyrrolidine with 1mol of concentrated hydrochloric acid, heating to 80 ℃, reacting for 8h, adding 1mol of aluminum chloride solution, heating to 80 ℃, and reacting for 6h to obtain the compound.

2. Preparation of graphene loaded nano magnesium oxide

And adding 10g of graphene oxide and 50g of magnesium oxide into water, performing ultrasonic dispersion for 4 hours at 80 ℃, and drying to obtain the graphene-loaded nano magnesium oxide.

3. Uniformly mixing 100g of 180# heavy oil, 10g N-methyl-N-ethyl pyrrolidine aluminum chloride ionic liquid and 4g of viscosity reduction dispersant (wherein the mass ratio of sulfonated styrene-maleic anhydride copolymer to secondary alkyl sodium sulfonate is 20: 8), stirring at 90 ℃ for 5h, adding 1g of graphene-loaded nano magnesium oxide, stirring at 70 ℃ for 3h, standing for layering after the reaction is finished, and separating the ionic liquid to obtain the clean fuel oil 3 #.

Comparative example 1 comparative clean Fuel oil 1#

The kind of the pyrrolidine ionic liquid adopted in the comparative example 1 is different from that of the example 1, the N-methylpyrrolidone aluminum chloride ionic liquid adopted in the comparative example 1 is the same as that of the example 1 in all other steps and all the material using amounts, and finally the comparative clean fuel oil 1# is prepared.

Comparative example 2 comparative clean Fuel oil 2#

The kind of the ionic liquid adopted in the comparative example 2 is different from that of the ionic liquid adopted in the example 1, the pyridine ionic liquid adopted in the comparative example 2 is N-methyl-N-propyl piperidine ferric bromide ionic liquid, other steps and the use amount of all the substances are the same as those in the example 1, and finally, the comparative clean fuel oil No. 2 is prepared.

Comparative example 3 comparative clean Fuel oil 3#

The mass ratio of the N-methyl-N-ethyl pyrrolidine aluminum chloride ionic liquid to the graphene-supported nano metal oxide in the comparative example 3 is different from that in the example 1, the mass ratio of the N-methyl-N-ethyl pyrrolidine aluminum chloride ionic liquid to the graphene-supported nano metal oxide in the comparative example 3 is 15:1, the other steps and the use amounts of all the substances are the same as those in the example 1, and the comparative clean fuel oil 3# is finally prepared.

Comparative example 4 comparative clean Fuel oil 4#

The mass ratio of the viscosity-reducing dispersant to the graphene-loaded nano metal oxide in comparative example 4 is different from that in example 1, the mass ratio of the viscosity-reducing dispersant to the graphene-loaded nano metal oxide in comparative example 4 is 8:1, the other steps and the use amounts of the substances are the same as those in example 1, and finally, comparative clean fuel oil No. 4 is prepared.

Comparative example 5 comparative clean Fuel oil 5#

The oxidation desorbent adopted in the comparative example 5 is different from that adopted in the example 1, the graphene-supported zirconia is adopted in the comparative example 5, other steps and the use amount of all substances are the same as those in the example 1, and finally, the comparative clean fuel oil No. 5 is prepared.

Comparative example 6 comparative clean Fuel oil 6#

Comparative example 6 was carried out without using an oxidizing adsorbent, and the other steps and the amounts of the substances were the same as those in example 1, to finally prepare comparative clean fuel oil # 6.

Comparative example 7 comparative clean Fuel oil 7#

Comparative example 7 No. 7 was carried out using the viscosity reducing dispersant, and the other steps and the amounts of the respective substances were the same as those in example 1, to finally prepare comparative clean fuel oil No. 7.

Comparative example 8 comparative clean Fuel oil 8#

The composition of the viscosity reducing dispersant in comparative example 8 is different from that in example 1, the ethylene-vinyl acetate copolymer adopted in comparative example 8, the other steps and the use amount of all substances are the same as those in example 1, and finally, comparative clean fuel oil No. 8 is prepared.

Example 4 desulfurization cleaning effect test

1. Desulfurization test

The test results of 180# heavy oil having 2.5% sulfur content, which was used in examples 1 to 3 and comparative examples 1 to 8, were as shown in Table 1, when examined using the GB/T380 standard.

2. Viscosity measurement

The detection method comprises the following steps: the kinematic viscosity was measured in accordance with GB/T11137 Standard, and 180# heavy oil having a sulfur content of 2.5% and a kinematic viscosity of 180mm at 50 ℃ was used in each of examples 1 to 3 and comparative examples 1 to 8²The test results are shown in Table 1.

TABLE 1

The results show that the clean fuel oil 1# -3# prepared by the desulfurization purification method of the embodiment 1-3 has reduced viscosity, remarkably reduced sulfur content, less than 0.5 percent of sulfur content and more than 80 percent of desulfurization rate, wherein the embodiment 1 achieves 92 percent of desulfurization rate.

In comparative examples 1 and 2, different ionic liquids were used, and the viscosities of the comparative clean fuel oil 1# and the comparative clean fuel oil 2# were reduced, but the desulfurization effect was general, and the desulfurization rate was about 60%.

Compared with the clean fuel oil 3#, the mass ratio of the ionic liquid to the oxidation desorbent is too high, the viscosity is reduced, but the desulfurization effect is poor, and the excessive ionic liquid influences the uniformity of the oxidation desorbent in the fuel oil and influences pi complexation to form a chemical bond; the mass ratio of the viscosity-reducing dispersant to the oxidation desorbent in the comparative example 4 is too high, and although the viscosity of the comparative clean fuel oil No. 4 is lower, the excessive sulfonated styrene-maleic anhydride copolymer can wrap the oxidation desorbent, so that the physical adsorption capacity and the chemical adsorption capacity of the oxidation desorbent are reduced.

In comparative example 5, other types of graphene-supported nano oxides are used, and in comparative example 6, no oxidation adsorbent is used, so that the finally obtained comparative clean fuel oil No. 5 and comparative clean fuel oil No. 6 have the advantages of medium viscosity, poor desulfurization effect and low desulfurization rate.

Comparative example 7 does not use a viscosity reducing dispersant, and comparative example 8 uses other types of copolymers, and the finally obtained comparative clean fuel oil 7# and comparative clean fuel oil 8# have high viscosities, poor fuel oil fluidity, poor desulfurization effect and low desulfurization rate.

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.