A nano-cerium dioxide-based fuel additive, a preparation method and application thereof

Abstract

The application provides a nano cerium dioxide-based fuel additive and a preparation method and application thereof. The preparation method of the nano cerium dioxide-based fuel additive comprises the following steps: mixing a ligand, a dispersing agent, a dissolving oil and an oil phase auxiliary agent to obtain an oil phase; mixing cerium halide, an aqueous phase solvent, an oxidizing agent and an alkalizing agent to obtain an aqueous phase; and reacting the oil phase and the aqueous phase by using a supergravity reaction method to obtain the nano cerium dioxide-based fuel additive. The nano cerium dioxide-based fuel additive can be stably dispersed in fuel.

Description

Technical Field

[0001] This invention belongs to the field of fuel additives, specifically relating to a fuel additive based on nano-cerium dioxide, its preparation method, and its application. Background Technology

[0002] Cerium dioxide possesses unique redox properties, readily undergoing valence state changes between Ce(III) and Ce(IV), accompanied by the absorption and release of oxygen. It exhibits high catalytic oxidation activity and can significantly reduce the combustion temperature of carbon soot in engine exhaust, thereby significantly reducing particulate matter emissions from the engine. Therefore, it has always been one of the main components of automotive engine exhaust purification catalysts, and research on Ce-containing automotive engine exhaust purification catalysts is currently one of the research hotspots in the field of engine design and development.

[0003] In the existing technology, cerium (Ce) additives are added to diesel fuel so that the combustion products contain cerium dioxide. Cerium dioxide can reduce the ignition temperature of particles in the exhaust gas to below 300°C, so that they can ignite and burn at the normal exhaust temperature of the diesel engine, thus enabling the diesel particulate filter (DPF) to be automatically regenerated under most operating conditions.

[0004] Although cerium dioxide is widely used in the purification of automotive engine exhaust, its long-term stable dispersion in diesel fuel remains a challenge when used directly as a diesel additive. The extremely fine grains of nanoparticles result in enormous surface energy, and coupled with the attractive forces between particles, there is a strong tendency for them to spontaneously aggregate. Over time, this can lead to the formation of large, blocky aggregates, which not only lose the functionality of the ultrafine particles but also cause abrasive wear.

[0005] CN115011402A discloses a low-viscosity energy-saving diesel engine oil based on cerium oxide nano-additives and its preparation method. The low-viscosity energy-saving diesel engine oil comprises the following components: cerium oxide nano-additives, base oil, monoalkenyl succinimide, diene succinimide, low-alkalinity synthetic calcium sulfonate, high-alkalinity synthetic magnesium sulfonate, thiophosphoric bis(octyl) basic zinc salt, N-phenyl-α-naphthylamine, ethylene glycol oleate, antifoaming agent T901, and viscosity index agent T602. This method provides a large-scale preparation method for cerium oxide nano-additives and a cerium oxide nano-additive diesel engine oil compounding technology, making the diesel engine oil suitable for various novel friction pairs, including nitriding, DLC coating, and cast iron, while simultaneously reducing the viscosity of the diesel engine oil and increasing its viscosity index. CN115417443A discloses nano-cerium oxide particles and their green synthesis process and application. The preparation of the nano-cerium oxide particles includes the preparation of plant extracts and the synthesis of nano-cerium oxide, wherein the plant is plantain or white clover. This preparation method is green and pollution-free, requires minimal equipment, and is easy to promote on a large scale. Summary of the Invention

[0006] To address the aforementioned problems, this invention provides a fuel additive based on nano-cerium dioxide, its preparation method, and its application. This nano-cerium dioxide-based fuel additive can be stably dispersed when added to fuel.

[0007] To achieve the above objectives, the present invention provides a method for preparing a fuel additive based on nano-cerium dioxide, comprising the following steps:

[0008] (1) Mix the ligand, dispersant, dissolving oil and oil phase aid to obtain the oil phase;

[0009] (2) Mix cerium halide, aqueous solvent, oxidant and alkalizing agent to obtain an aqueous phase;

[0010] (3) The oil phase and the water phase are reacted by a supergravity reaction method to obtain the fuel additive based on nano-cerium dioxide.

[0011] According to a specific embodiment of the present invention, preferably, in the above preparation method, the ligand includes one or more of the following: derivatives of ethylenediamine, derivatives of 2,2'-bipyridine, derivatives of 1,10-o-diazaphenanthroline, derivatives of oxalic acid, derivatives of ethylenediaminetetraacetic acid, and derivatives of salicylaldehyde imine; more preferably, it includes one or more of the following: alkylated derivatives of ethylenediamine, alkylated derivatives of 2,2'-bipyridine, alkylated derivatives of 1,10-o-diazaphenanthroline, alkylated derivatives of oxalic acid, alkylated derivatives of ethylenediaminetetraacetic acid, and alkylated derivatives of salicylaldehyde imine; and even more preferably, it includes one or more of the following: alkylated derivatives of ethylenediamine and / or derivatives of salicylaldehyde imine, or combinations thereof.

[0012] According to a specific embodiment of the present invention, preferably, in the above preparation method, the alkylated derivative includes C3-C20 alkyl monosubstituted derivatives and / or C3-C20 alkyl disubstituted derivatives.

[0013] According to a specific embodiment of the present invention, preferably, the ligand salicylaldehyde imine derivative is prepared by reacting a long-chain substituted imine with salicylaldehyde to increase the oil solubility of the ligand. The synthetic route is as follows:

[0014]

[0015] Where R is a C3-C20 alkyl group;

[0016] Furthermore, the salicylaldehyde imine derivative forms a coordination compound with the cerium salt, and this complex is stably dispersed in the oil under the action of a dispersant.

[0017] According to a specific embodiment of the present invention, preferably, in the above preparation method, the rotation speed in the hypergravity reaction method is 1000 r / min to 5000 r / min, more preferably 1500 r / min to 2500 r / min.

[0018] According to a specific embodiment of the present invention, preferably, in the above preparation method, the dispersant includes one or more of oleic acid, polysorbate, sorbitan oleate, succinimide and its derivatives; more preferably, the polysorbate includes one or more of Tween-20, Tween-40, Tween-60, Tween-80, and Tween-85, the sorbitan oleate includes one or more of Sben 20, Sben 40, Sben 60, Sben 80, and Sben 85, and the succinimide derivative includes one or more of diene succinimide (T152), polyisobutylene bis(succinimide) (T154), and high molecular weight succinimide (T161).

[0019] According to a specific embodiment of the present invention, preferably, in the above preparation method, the dissolving oil includes one or more of the following: fuel oil, API Group I base oil, API Group II base oil, API Group III base oil, API Group IV base oil, and API Group V base oil.

[0020] According to a specific embodiment of the present invention, preferably, in the above preparation method, the kinematic viscosity of the dissolved oil at 40°C is 5 mm. 2 / s to 50mm 2 / s.

[0021] According to a specific embodiment of the present invention, preferably, the above preparation method satisfies one or more of the following conditions:

[0022] (1) The oil phase additives include one or a combination of two of petroleum ether and light white oil;

[0023] (2) The oxidizing agent includes hydrogen peroxide;

[0024] (3) The alkalizing agent includes one or more of ammonia, triethanolamine, diethanolamine, monoethanolamine, diethylene glycolamine, and diisopropanolamine;

[0025] (4) The mass ratio of the dissolving oil to the oil phase additive is 1-5:1; more preferably 1-2:1;

[0026] (5) The mass ratio of the dispersant to the ligand is 1:1-4; more preferably 1:2;

[0027] (6) The mass ratio of the ligand to the dissolving oil is 1:1-8;

[0028] (7) The ratio of the mass of the aqueous solvent to the sum of the masses of the oxidant and the alkalizing agent is 1-5:1; more preferably 1-2:1;

[0029] (8) The ratio of the mass of the cerium halide to the sum of the masses of the oxidant and the alkalizing agent is 2-10:1; more preferably 6-8:1;

[0030] (9) The mass ratio of cerium halide to ligand is 1:2-10; more preferably 1:4-6;

[0031] (10) In the supergravity reaction method, the pumping speed ratio of the oil phase and the water phase is 4-20:1, more preferably 8-20:1.

[0032] The present invention does not particularly limit the mass ratio of oxidant to alkalizing agent. According to a specific embodiment of the present invention, preferably, the mass ratio of oxidant to alkalizing agent is (1-3):1.

[0033] According to a specific embodiment of the present invention, the above preparation method includes the following specific steps:

[0034] At room temperature, ligands, dispersants, and dissolving oil are dissolved in petroleum ether to form an oil phase, which is pumped into a high-gravity reactor through the oil phase inlet. Simultaneously, an aqueous mixed solution is pumped in through the aqueous phase inlet. Both materials are sprayed onto the inner surface of a core rotating at high speed using spray pipes. Under centrifugal force, the materials enter the core packing radially and move towards the outer edge of the packing. The materials inside the core are cut into tiny droplets by the high-speed rotating packing. Pressurized air is introduced into the core through the reactor inlet, suspending and dispersing the droplets within the packing, ensuring thorough and uniform contact between the two types of droplets until the reaction ends after a certain period. After the reaction, the product is centrifuged at 5000 r / min for 30 min. The upper oily layer is separated and washed three times with deionized water to remove reaction residues. The final oily substance is collected using a separatory funnel, and the remaining petroleum ether is distilled off to obtain the final product.

[0035] The present invention also provides a fuel additive based on nano-cerium dioxide, which is prepared by the above preparation method.

[0036] The present invention also provides the application of the above-mentioned nano-cerium dioxide-based fuel additive as an additive in fuel.

[0037] The present invention also provides a fuel comprising the above-mentioned fuel additive based on nano-cerium dioxide.

[0038] According to a specific embodiment of the present invention, preferably, the mass fraction of the fuel additive based on nano-cerium dioxide in the fuel is 20-1000 ppm, more preferably 40-100 ppm.

[0039] According to a specific embodiment of the present invention, preferably, the fuel includes automotive gasoline conforming to GB 17930-2016 standard and / or automotive diesel conforming to GB 19147 standard.

[0040] This invention uses an in-situ method under a supergravity field to prepare a fuel additive based on nano-cerium dioxide. The nanoparticles have a uniform size distribution, high yield, and good storage stability at room temperature. When added to fuel, it can be stably dispersed in the fuel for a long time, which can save fuel in the engine and reduce harmful emissions, such as THC, PM, and smoke. Detailed Implementation

[0041] In order to provide a clearer understanding of the technical features, objectives and beneficial effects of the present invention, the technical solution of the present invention will now be described in detail below, but it should not be construed as limiting the scope of implementation of the present invention.

[0042] Where specific techniques or conditions are not specified in the examples, they shall be performed in accordance with the techniques or conditions described in the prior art or in accordance with the product instructions. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0043] The centrifugal reactors used below are rotating packed bed reactors with a rotation speed range of 800-8000 rpm.

[0044] Example 1

[0045] This embodiment provides a fuel additive based on nano-cerium dioxide, which is prepared by the following steps:

[0046] At room temperature (25℃), the oil phase solutions shown in Table 1 were mixed thoroughly and pumped into the high-gravity reactor through the oil phase inlet. Simultaneously, the aqueous phase solution was pumped in through the aqueous phase inlet, with a pumping rate ratio of 8:1 between the oil and aqueous phases. Both materials were sprayed onto the inner surface of a rotating core at a high speed of 2000 r / min using a spray pipe, and the reaction was allowed to proceed for 2 hours. After the reaction, the product was centrifuged at 5000 r / min for 30 minutes. The upper oily layer was separated and washed three times with deionized water to remove reaction residues. The final oily substance was collected using a separatory funnel, and the residual petroleum ether was distilled off to obtain the fuel additive product based on nano-cerium dioxide. The ligand used in this embodiment is a salicylaldehyde imine derivative (CAS: 103595-82-0). This ligand can also be synthesized according to the preparation method in Section 1.2 of “Cheng Zhengzai, Zhang Weixing, Gong Kai, Cong Ye, Chen Hongxiang, Li Wenbing. Synthesis of novel salicylaldehyde imine titanium complex and catalytic polymerization of ethylene [J]. 2015, 29(6):453-462”.

[0047] Table 1

[0048]

[0049] Example 2

[0050] This embodiment provides a fuel additive based on nano-cerium dioxide. Its preparation method is the same as that in Example 1, except that the engine speed is 1000 r / min. The formula is shown in Table 2.

[0051] Table 2

[0052]

[0053]

[0054] Example 3

[0055] This embodiment provides a fuel additive based on nano-cerium dioxide, which is prepared in the same way as in Example 1, except that the ligand is 4,4'-dinonyl-2,2'-bipyridine (CAS: 142646-58-0), and the formulation is shown in Table 3.

[0056] Table 3

[0057]

[0058] Example 4

[0059] This embodiment provides a fuel additive based on nano-cerium dioxide, which is prepared in the same way as in Example 1, except that the dispersant is polyisobutylene succinimide, and the formula is shown in Table 4.

[0060] Table 4

[0061]

[0062]

[0063] Example 5

[0064] This embodiment provides a fuel additive based on nano-cerium dioxide, which is prepared in the same way as in Example 1, except that the cerium halide salt is cerium bromide, and the formula is shown in Table 5.

[0065] Table 5

[0066]

[0067] Comparative Example 1

[0068] This comparative example provides a fuel additive based on nano-cerium dioxide, which is prepared in the same way as in Example 1, except that the rotation speed is 8000 r / min.

[0069] Comparative Example 2

[0070] This comparative example provides a fuel additive based on nano-cerium dioxide, which is prepared in the same way as in Example 2, except that the rotation speed is 500 r / min.

[0071] Comparative Example 3

[0072] This comparative example provides a fuel additive based on nano-cerium dioxide, which is prepared in the same way as in Example 4, except that the dispersant is isopropanol.

[0073] Comparative Example 4

[0074] This comparative example provides a fuel additive based on nano-cerium dioxide, which is prepared in the same way as in Example 5, except that the dissolving oil is HVIS150BS.

[0075] The test results of the fuel additives in Examples 1-5 and Comparative Examples 1-4 are shown in Table 6 below. The particle size was tested using a nanoparticle size analyzer, and the storage stability was tested by observing the samples stored at room temperature.

[0076] Table 6

[0077]

[0078] In Table 6, the yield = (actual Ce content in the product / theoretical maximum Ce content) × 100%.

[0079] As shown in Table 6, the fuel additive of the present invention can ensure a fuel additive yield of over 95% while maintaining a nanoparticle size between 5-30 nm.

[0080] Example 6

[0081] The fuel additive obtained in Example 1 was added at a ratio of 50 ppm to No. 0 diesel fuel that meets the requirements of GB 19147 "Automotive Diesel Fuel" to obtain fuel A with added fuel additive.

[0082] Example 7

[0083] The fuel additive obtained in Example 1 was added at a ratio of 50 ppm to 95-octane gasoline that meets the requirements of GB 17930 "Automotive Gasoline" to produce fuel B with added fuel additive.

[0084] Comparative Example 5

[0085] Similar to Example 6, except that cerium dioxide (CAS: 1306-38-3) is directly added to diesel fuel as a fuel additive to obtain fuel C with added cerium dioxide.

[0086] Comparative Example 6

[0087] Similar to Example 7, except that 95-octane gasoline is replaced with No. 1 kerosene that meets GB 253 "kerosene" to produce fuel D with added fuel additives.

[0088] Under an engine speed of 2000 r / min, the speed characteristics, stability, and harmful emissions of Examples 6-7 and Comparative Examples 5-6 were compared (the data in Table 7 represent the percentage difference between the test values ​​of fuels A-D and the corresponding blank fuel test values). Harmful emissions were tested according to standard GB 17691. External characteristic tests were conducted at the maximum throttle (calibrated external characteristics) and 2 / 3 throttle (partial external characteristics) of the diesel engine, during which the engine speed, power, torque, fuel consumption rate, and exhaust temperature were measured. Operational stability tests were conducted at 2000 r / min, 2 / 3 throttle opening, and 1 / 2 throttle opening, during which the diesel engine power, fuel consumption rate, and exhaust temperature were measured. The test diesel engine was a Phaser140Ti-E30, a four-cylinder, in-line, water-cooled, four-stroke, high-pressure common rail electronic diesel injection engine with a bore of 100mm, stroke of 127mm, displacement of 3.99L, an "ω"-type combustion chamber, rated power of 90KW, and rated speed of 2500r / min. The hydraulic dynamometer was a WE33H model, manufactured by Hangzhou Yike Electromechanical Co., Ltd. The smoke meter was a 415S G002 model, manufactured by AVL GmbH, Austria. The gas analyzer was a MEXA-7100DEGR model, manufactured by HORIBA GmbH, Japan. The particulate matter collection system was an MDLT-1302TMA model, manufactured by HORIBA GmbH, Japan.

[0089] Table 7

[0090]

[0091] As shown in Table 7, the fuel with the additive of the present invention exhibits significantly improved speed characteristics and operational stability, and significantly reduced harmful emissions of THC, smoke, and PM. However, directly using non-nano-grade cerium dioxide as an additive, or applying the fuel additive provided in this invention to fuels other than gasoline and diesel, does not significantly improve the fuel's speed characteristics, operational stability, or harmful emissions.

Claims

1. A method for preparing a fuel additive based on nano-cerium dioxide, comprising the following steps: (1) Mix the ligand, dispersant, dissolving oil and oil phase aid to obtain the oil phase; (2) Mix cerium halide, aqueous solvent, oxidant and alkalizing agent to obtain an aqueous phase; (3) The oil phase and the water phase are reacted by a supergravity reaction method to obtain the fuel additive based on nano-cerium dioxide.

2. The preparation method according to claim 1, wherein, The ligands include one or more of the following: derivatives of ethylenediamine, derivatives of 2,2'-bipyridine, derivatives of 1,10-o-diazaphenanthroline, derivatives of oxalic acid, derivatives of ethylenediaminetetraacetic acid, and derivatives of salicylaldehyde imine.

3. The preparation method according to claim 2, wherein, The ligands include one or more of the following: alkylated derivatives of ethylenediamine, alkylated derivatives of 2,2'-bipyridine, alkylated derivatives of 1,10-o-diazaphenanthroline, alkylated derivatives of oxalic acid, alkylated derivatives of ethylenediaminetetraacetic acid, and alkylated derivatives of salicylaldehyde imine.

4. The preparation method according to claim 3, wherein, The alkylated derivatives include C3-C20 mono-substituted alkyl derivatives and / or C3-C20 di-substituted alkyl derivatives.

5. The preparation method according to claim 1, wherein, In the hypergravity reaction method, the rotation speed is 1000 r / min to 5000 r / min; And / or, the dispersant comprises one or more of oleic acid, polysorbate, sorbitan oleate, succinimide and its derivatives; And / or, the dissolved oil includes one or more of the following: fuel oil, API Group I base oil, API Group II base oil, API Group III base oil, API Group IV base oil, and API Group V base oil.

6. The preparation method according to any one of claims 1-5, wherein, The preparation method satisfies one or more of the following conditions: (1) The oil phase additives include one or a combination of two of petroleum ether and light white oil; (2) The oxidizing agent includes hydrogen peroxide; (3) The alkalizing agent includes one or more of ammonia, triethanolamine, diethanolamine, monoethanolamine, diethylene glycolamine, and diisopropanolamine; (4) The mass ratio of the dissolving oil to the oil phase additive is 1-5:1; (5) The mass ratio of the dispersant to the ligand is 1:1-4; (6) The mass ratio of the ligand to the dissolving oil is 1:1-8; (7) The ratio of the mass of the aqueous solvent to the sum of the masses of the oxidant and the alkalizing agent is 1-5:1; (8) The ratio of the mass of the cerium halide to the sum of the masses of the oxidizing agent and the alkalizing agent is 2-10:1; (9) The mass ratio of the cerium halide to the ligand is 1:2-10; (10) In the supergravity reaction method, the pumping speed ratio of the oil phase and the water phase is 4-20:

1.

7. A fuel additive based on nano-cerium dioxide, which is prepared by the preparation method according to any one of claims 1-6.

8. The application of the fuel additive based on nano-cerium dioxide as described in claim 7 as an additive in fuel.

9. A fuel oil comprising the fuel additive based on nano-cerium dioxide as described in claim 7.

10. The fuel oil according to claim 9, wherein, The mass fraction of the fuel additive based on nano-cerium dioxide in the fuel is 20-1000 ppm.

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