Diesel liquid nano-additive and preparation method thereof

Abstract

This invention discloses a diesel liquid nano-additive and its preparation method, comprising the following components by mass percentage: 0.02-0.5% rare earth-based nano-catalyst, 52-67% cetane number improver, 1-5% smoke suppressant, 3-19% detergent-dispersant, 3-8% pour point depressant, 7-20% antioxidant, and 5-13% lubricant. This invention enables catalytic combustion of diesel fuel, simultaneously promoting the combustion of CO, HC, and soot, reducing particulate matter formation during the main combustion period, lowering exhaust pollutant emissions, ultimately achieving energy savings, enhanced power, ultra-low exhaust emissions, and significantly improving the calorific value of diesel fuel, achieving an energy-saving efficiency of over 37%, demonstrating significant energy-saving effects.

Description

Technical Field

[0001] This invention belongs to the field of diesel additive technology, specifically relating to a diesel liquid nano-additive and its preparation method. Background Technology

[0002] Global warming is a consequence of human activities impacting Earth's climate change, with carbon dioxide being the primary culprit. Automobiles are the main contributors to total pollutant emissions, accounting for over 90% of carbon monoxide (CO), hydrocarbons (HC), nitrogen oxides (NOx), and particulate matter / smoke (PM) emissions. Diesel vehicles account for over 80% of total NOx emissions and over 90% of total PM emissions from automobiles, highlighting the increasing urgency of controlling pollution from mobile sources. With the goals of energy conservation, pollution reduction, and environmental improvement, improving diesel combustion efficiency to reduce energy consumption and pollution has become a key research focus.

[0003] There are many ways to improve diesel combustion efficiency and reduce exhaust pollution. Currently, using diesel additives is one of the most effective and economical methods. Without modifying the vehicle and engine structure or adding equipment, it can improve fuel combustion performance and reduce harmful emissions. The principle is to add certain active components to change the combustion mechanism, promote fuel combustion, and simultaneously promote the combustion of CO, HC, and PM, thereby reducing exhaust pollutant emissions. Previous research has largely focused on single-component organic compounds such as alcohols, ethers, and esters with high oxygen content. However, these additives have limitations, including limited variety, large dosage requirements, and limited improvement in diesel quality. Therefore, the research and development of multifunctional composite diesel additives has received widespread attention. Composite diesel additives generally include the following components: cetane number improvers, detergents and dispersants, pour point depressants, antioxidants, lubricants, and combustion catalysts. Among these, combustion catalysts are the most widely studied by researchers both domestically and internationally because they accelerate fuel atomization and evaporation, promote uniform mixing with air, and achieve rapid and complete combustion, thus reducing fuel consumption and pollutant emissions. Numerous studies have shown that the use of cerium-based diesel additives can reduce the peak concentration of diesel fuel, lower the ignition temperature, and simultaneously increase the oxidation rate. CeO2, due to its Ce... 4+ / Ce 3+ CeO2's valence states can interconvert, and it possesses oxygen storage / release capabilities as well as excellent stability, giving it a unique role in catalytic combustion chemistry and exhaust gas purification. Using CeO2 as a support to load active metals such as nickel, iron, manganese, zinc, copper, cobalt, gold, silver, and platinum can further enhance the catalytic activity of the catalyst, slow down catalyst deactivation, and extend its service life.

[0004] CN113684072A discloses an additive for improving diesel fuel combustion and its preparation method, comprising the following components in parts by weight: 15-20 parts polyethylene glycol nitrate, 8-12 parts tetrahydrofuran nitrate, 5-10 parts ethylene glycol nitrate, 15-20 parts ethanolamine, 6-9 parts long-chain fatty acid methyl ester, 1-5 parts isooctyl nitrate, 5-10 parts polyisobutylene succinamide, 8-12 parts nano-additive, 5-8 parts low-temperature flow agent, 6-12 parts combustion aid, and 1-5 parts metal salt. However, the nano-additive prepared by this technical solution is only CeO2, resulting in poor catalyst activity. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide a diesel liquid nano-additive and its preparation method.

[0006] The technical solution of the present invention is as follows:

[0007] A diesel fuel nano-additive comprises the following components by weight percentage: 0.02-0.5% rare earth-based nano-catalyst, 52-67% cetane number improver, 1-5% smoke suppressant, 3-19% detergent-dispersant, 3-8% pour point depressant, 7-20% antioxidant, and 5-13% lubricant, wherein...

[0008] The antioxidant is 2,6-di-tert-butylphenol mixture.

[0009] Rare earth-based nanocatalysts comprise a support and a catalytic metal supported on the support. The support is porous nano-CeO2 obtained by high-temperature calcination of a Ce-based metal-organic framework material. The porous nano-CeO2 has a particle size of 10-1000 nm and a specific surface area of ​​100-150 m². 2 g -1 The total pore volume is 0.1-0.5 cm³. 3 g -1 The loading of the catalytic metal is 1-6 wt% of the support.

[0010] In a preferred embodiment of the present invention, the catalytic metal is at least one selected from nickel, iron, manganese, zinc, copper, cobalt, gold, silver and platinum.

[0011] In a preferred embodiment of the present invention, the cetane number improver is at least one of isooctyl nitrate, dimethoxyethane, and ethyl lactate.

[0012] In a preferred embodiment of the present invention, the smoke suppressant is at least one of ferrocene, barium sulfate, tetrahydrofuran, and ethyl nitrate.

[0013] In a preferred embodiment of the present invention, the cleaning and dispersing agent is at least one selected from succinimide, tetrahydronaphthalene, and alkyl salicylate calcium.

[0014] In a preferred embodiment of the present invention, the pour point depressant is a polyethylene fumarate copolymer and / or an ethylene-vinyl acetate copolymer.

[0015] In a preferred embodiment of the present invention, the lubricant is a long-chain fatty acid methyl ester and / or ethylene glycol dinitrate.

[0016] The preparation method of the above-mentioned diesel liquid nano-additive includes the following steps:

[0017] (1) Pour the rare earth-based nanocatalyst into the cetane number improver, then add the surfactant, ultrasonically vibrate for 0.5-2h until completely dispersed, then stir and mix at a speed of 200-350r / min for 30-50min, and let stand naturally for 30-60min.

[0018] (2) Add lubricant, antioxidant, pour point depressant and detergent dispersant to the material obtained in step (1), and stir and mix at a speed of 120-250 r / min for 20-40 min;

[0019] (3) Add smoke suppressant to the material obtained in step (2), stir and mix at a speed of 100-400 r / min for 60-90 min until completely dissolved, and then let it stand naturally for 1-2 h to obtain the diesel liquid nano additive.

[0020] In a preferred embodiment of the present invention, the surfactant is at least one selected from hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, and sodium dodecyl sulfate.

[0021] In a preferred embodiment of the present invention, the mass ratio of the surfactant to the rare earth-based nanocatalyst is 2-10:1.

[0022] The beneficial effects of this invention are:

[0023] 1. This invention utilizes Ce-based metal-organic framework materials as templates / precursors to prepare nano-CeO2 through high-temperature calcination. Compared with commercial CeO2, the porous nano-CeO2 evolved from the organic framework material possesses a large specific surface area, abundant active sites, excellent catalytic performance, and good dispersibility. Furthermore, using porous nano-CeO2 as a support to load active metals such as nickel, iron, manganese, zinc, copper, cobalt, gold, silver, and platinum further significantly enhances the catalytic activity.

[0024] 2. This invention can achieve catalytic combustion of diesel fuel, while promoting the combustion of CO, HC and soot, reducing the formation of particulate matter during the main combustion period, reducing exhaust pollutant emissions, and ultimately achieving energy saving, enhanced power and ultra-low exhaust emissions.

[0025] 3. This invention significantly increases the calorific value of diesel fuel, achieving an energy-saving efficiency of over 37%, thus demonstrating a remarkable energy-saving effect. Detailed Implementation

[0026] The technical solution of the present invention will be further explained and described below through specific embodiments.

[0027] Example 1

[0028] 5 mg of nickel nitrate was dissolved in 5 mL of water, and 20 mg of nano-CeO2 carrier was added. The CeO2 particles had a diameter of 50 nm and a specific surface area of ​​110 m². 2 g -1 The total pore volume is 0.1 cm³. 3 g -1 The catalyst was stirred thoroughly at room temperature for 6 hours, evaporated to dryness in a water bath at 80°C, dried at 60°C for 9 hours, ground thoroughly, calcined in air at 450°C for 5 hours, and finally reduced with H2 at 450°C for 2 hours to obtain Ni (5wt%) / CeO2 nanocatalyst.

[0029] The above-mentioned Ni (5wt%) / CeO2 nanocatalyst and 40 mg of cetyltrimethylammonium bromide were poured into 63 g of dimethoxyethane and oscillated in an ultrasonic oscillator for 1 h until completely dispersed. Then, it was added to a raw material mixing tank and stirred at 250 r / min for 30 min, and allowed to stand naturally for 30 min. Then, 9 g of ethylene glycol dinitrate, 16 g of 2,6-di-tert-butyl phenol mixture, 5 g of ethylene-vinyl acetate copolymer, and 5 g of tetrahydronaphthalene were added to the raw material mixing tank and stirred at 200 r / min for 30 min. Finally, 1 g of ferrocene and 1 g of barium sulfate were added and stirred at 250 r / min for 70 min until completely dissolved. After standing naturally for 1 h, the diesel liquid nano-additive was obtained.

[0030] Example 2

[0031] Dissolve 6 mg of nickel nitrate in 5 mL of water, then add 20 mg of nano-CeO2 support. The CeO2 particles have a diameter of 100 nm and a specific surface area of ​​120 m². 2 g -1 The total pore volume is 0.3 cm³. 3 g -1The catalyst was stirred thoroughly at room temperature for 7 hours, evaporated to dryness in a water bath at 80°C, dried at 60°C for 10 hours, ground thoroughly, calcined in air at 450°C for 5 hours, and finally reduced with H2 at 450°C for 2 hours to obtain Ni (6wt%) / CeO2 nanocatalyst.

[0032] The above-mentioned Ni (6wt%) / CeO2 nanocatalyst and 80 mg of hexadecyltrimethylammonium chloride were poured into 50 g of dimethoxyethane and oscillated in an ultrasonic oscillator for 1 h until completely dispersed. Then, it was added to a raw material mixing tank and stirred at 300 r / min for 30 min, and allowed to stand naturally for 40 min. Then, 13 g of long-chain fatty acid methyl ester, 20 g of 2,6-di-tert-butyl mixed phenol, 7 g of ethylene-vinyl acetate copolymer, 5 g of succinimide, and 4 g of alkyl salicylate were added to the raw material mixing tank and stirred at 180 r / min for 40 min. Finally, 1 g of tetrahydrofuran was added and stirred at 300 r / min for 65 min until completely dissolved. After standing naturally for 1 h, the diesel liquid nano-additive was obtained.

[0033] Example 3

[0034] Dissolve 7.5 mg of ferric nitrate in 5 mL of water, then add 30 mg of nano-CeO2 carrier. The CeO2 particles have a diameter of 100 nm and a specific surface area of ​​120 m². 2 g -1 The total pore volume is 0.3 cm³. 3 g -1 The Fe(5wt%) / CeO2 nanocatalyst was prepared by stirring thoroughly at room temperature for 8 hours, evaporating in a water bath at 80℃, drying at 70℃ for 9 hours, grinding thoroughly, calcining in air at 450℃ for 5 hours, and finally reducing with H2 at 450℃ for 2 hours.

[0035] The above-mentioned Fe (5wt%) / CeO2 nanocatalyst and 120 mg cetyltrimethylammonium bromide were added to 36 g isooctyl nitrate and 25 g ethyl lactate, and the mixture was ultrasonically vibrated for 1 h until completely dispersed. Then, it was added to a raw material mixing tank and stirred at 300 r / min for 50 min, and allowed to stand naturally for 60 min. Then, 13 g ethylene glycol dinitrate, 11 g 2,6-di-tert-butyl phenol, 8 g polyethylene fumaric acid copolymer, and 5 g tetrahydronaphthalene were added to the raw material mixing tank and stirred at 180 r / min for 30 min. Finally, 2 g tetrahydrofuran was added and stirred at 250 r / min for 90 min until completely dissolved. The mixture was allowed to stand naturally for 2 h to obtain a diesel liquid nano-additive.

[0036] Example 4

[0037] 14 mg of ferric nitrate was dissolved in 10 mL of water, and 70 mg of nano-CeO2 carrier was added. The CeO2 particles had a diameter of 500 nm and a specific surface area of ​​130 m². 2 g -1 The total pore volume is 0.4 cm³. 3 g -1 The Fe(4wt%) / CeO2 nanocatalyst was prepared by stirring thoroughly at room temperature for 6 hours, evaporating in a water bath at 80℃, drying at 70℃ for 10 hours, grinding thoroughly, calcining in air at 450℃ for 5 hours, and finally reducing with H2 at 450℃ for 2 hours.

[0038] The above-mentioned Fe (4wt%) / CeO2 nanocatalyst and 140 mg sodium dodecyl sulfate were added to 56 g ethyl lactate and oscillated in an ultrasonic oscillator for 2 h until completely dispersed. Then, it was added to a raw material mixing tank and stirred at 300 r / min for 50 min, and allowed to stand naturally for 60 min. Then, 10 g ethylene glycol dinitrate, 12 g 2,6-di-tert-butyl phenols, 6 g ethylene-vinyl acetate copolymer, 7 g succinimide, and 5 g tetrahydronaphthalene were added to the raw material mixing tank and stirred at 250 r / min for 35 min. Finally, 2 g ferrocene and 2 g ethyl nitrate were added and stirred at 350 r / min for 80 min until completely dissolved. After standing naturally for 2 h, the diesel liquid nano-additive was obtained.

[0039] Example 5

[0040] 2 mg of cobalt nitrate was dissolved in 5 mL of water, and 20 mg of nano-CeO2 carrier was added. The CeO2 particles had a diameter of 500 nm and a specific surface area of ​​130 m². 2 g -1 The total pore volume is 0.4 cm³. 3 g -1 The catalyst was stirred thoroughly at room temperature for 6 hours, evaporated to dryness in a water bath at 85°C, dried at 80°C for 9 hours, ground thoroughly, calcined in air at 500°C for 5 hours, and finally reduced with H2 at 600°C for 2 hours to obtain Co (2wt%) / CeO2 nanocatalyst.

[0041] The above-mentioned Co (2wt%) / CeO2 nanocatalyst and 80 mg sodium dodecyl sulfate were poured into 61 g ethyl lactate and oscillated in an ultrasonic oscillator for 1.5 h until completely dispersed. Then, it was added to a raw material mixing tank and stirred at 280 r / min for 30-50 min, and allowed to stand naturally for 50 min. Then, 9 g long-chain fatty acid methyl ester, 14 g 2,6-di-tert-butyl mixed phenol, 7 g ethylene-vinyl acetate copolymer, and 6 g succinimide were added to the raw material mixing tank and stirred at 200 r / min for 40 min. Finally, 3 g ferrocene was added and stirred at 250 r / min for 70 min until completely dissolved. After standing naturally for 2 h, the diesel liquid nano-additive was obtained.

[0042] Example 6

[0043] 2.1 mg of manganese nitrate was dissolved in 5 mL of water, and 40 mg of nano-CeO2 carrier was added. The CeO2 particles had a diameter of 200 nm and a specific surface area of ​​125 m². 2 g -1 The total pore volume is 0.3 cm³. 3 g -1 The catalyst was stirred thoroughly at room temperature for 8 hours, evaporated to dryness in a water bath at 80°C, dried at 80°C for 9 hours, ground thoroughly, calcined in air at 500°C for 5 hours, and finally reduced with H2 at 600°C for 3 hours to obtain Mn(1wt%) / CeO2 nanocatalyst.

[0044] The above-mentioned Mn(1wt%) / CeO2 nanocatalyst and 160mg hexadecyltrimethylammonium chloride were added to 56g dimethoxyethane and ultrasonically vibrated for 1h until completely dispersed. Then, it was added to a raw material mixing tank and stirred at 300r / min for 30min, and allowed to stand naturally for 40min. Then, 10g ethylene glycol dinitrate, 16g 2,6-di-tert-butyl phenol, 8g polyethylene fumaric acid copolymer, and 9g tetrahydronaphthalene were added to the raw material mixing tank and stirred at 200r / min for 30min. Finally, 1g ethyl nitrate was added and stirred at 200r / min for 60min until completely dissolved. After standing naturally for 1.5h, the diesel liquid nano-additive was obtained.

[0045] Example 7

[0046] 4 mg of zinc nitrate was dissolved in 5 mL of water, and 30 mg of nano-CeO2 carrier was added. The CeO2 particles had a diameter of 600 nm and a specific surface area of ​​140 m². 2 g -1 The total pore volume is 0.4 cm³. 3 g -1The Zn(3wt%) / CeO2 nanocatalyst was prepared by stirring thoroughly at room temperature for 8 hours, evaporating to dryness in a water bath at 80℃, drying at 80℃ for 9 hours, grinding thoroughly, calcining in air at 450℃ for 4 hours, and finally reducing with H2 at 450℃ for 1 hour.

[0047] The above-mentioned Zn (3wt%) / CeO2 nanocatalyst and 150 mg cetyltrimethylammonium bromide were added to 35 g dimethoxyethane and 30 g isooctyl nitrate and oscillated in an ultrasonic oscillator for 1 h until completely dispersed. Then, it was added to a raw material mixing tank and stirred at 300 r / min for 30 min, and allowed to stand naturally for 60 min. Then, 3 g long-chain fatty acid methyl ester, 2 g ethylene glycol dinitrate, 12 g 2,6-di-tert-butyl mixed phenols, 5 g polyethylene fumaric acid copolymer, 5 g succinimide, and 5 g tetrahydronaphthalene were added to the raw material mixing tank and stirred at 200 r / min for 30 min. Finally, 2 g ferrocene and 1 g ethyl nitrate were added and stirred at 280 r / min for 80 min until completely dissolved. After standing naturally for 2 h, a diesel liquid nano-additive was obtained.

[0048] Example 8

[0049] Dissolve 1.1 mg of platinum nitrate in 5 mL of water, then add 70 mg of nano-CeO2 support. The CeO2 particles have a diameter of 700 nm and a specific surface area of ​​145 m². 2 g -1 The total pore volume is 0.4 cm³. 3 g -1 The Pt (1wt%) / CeO2 nanocatalyst was prepared by stirring thoroughly at room temperature for 8 hours, evaporating in a water bath at 90℃, drying at 60℃ for 12 hours, grinding thoroughly, calcining in air at 500℃ for 4 hours, and finally reducing with H2 at 700℃ for 3 hours.

[0050] The above-mentioned Pt (1wt%) / CeO2 nanocatalyst and 140mg sodium dodecyl sulfate were added to 33g dimethoxyethane and 25g ethyl lactate, and the mixture was ultrasonically vibrated for 2 hours until completely dispersed. Then, it was added to a raw material mixing tank and stirred at 350r / min for 50 minutes, and allowed to stand naturally for 30 minutes. Then, 6g long-chain fatty acid methyl ester, 6g ethylene glycol dinitrate, 12g 2,6-di-tert-butyl mixed phenols, 3g polyethylene fumaric acid copolymer, 3g ethylene-vinyl acetate copolymer, 2g succinimide, and 8g alkyl salicylate were added to the raw material mixing tank and stirred at 250r / min for 40 minutes. Finally, 1g ferrocene and 1g ethyl nitrate were added and stirred at 400r / min for 90 minutes until completely dissolved. The mixture was allowed to stand naturally for 2 hours to obtain a diesel liquid nano-additive.

[0051] Example 9

[0052] To further determine the performance of the diesel liquid nano-additives prepared in Examples 1 to 8 of the present invention, the following experiments are conducted to further illustrate the results.

[0053] Experimental methods:

[0054] 1. The density, viscosity, pH value, flash point, auto-ignition point and other important parameters of the diesel liquid nano-additives prepared in Examples 1 to 8 were accurately detected using relevant instruments and equipment. The specific parameters and experimental methods are shown in Table 1 and the parameter results are shown in Table 2.

[0055] 2. Combustion tests were conducted on diesel fuel alone, and the calorific value was measured using an oxygen bomb calorimeter. The diesel liquid nano-additives prepared in Examples 1 to 8 were then premixed with diesel fuel, and combustion tests were performed under the same conditions using the method described above. The results are shown in Table 3.

[0056] Table 1 Physicochemical parameters of diesel liquid nano-additives

[0057]

[0058]

[0059] Table 2 Physicochemical parameters of the diesel liquid nano-additive prepared in this invention

[0060]

[0061] Table 3. Determination of the energy-saving effect of the liquid nano-additive prepared in this invention.

[0062]

[0063]

[0064] The above experimental results show that the physicochemical properties of the diesel liquid nano-additives prepared in Examples 1 to 8 of this invention all meet the standards. Compared with diesel alone, the calorific value is significantly improved after mixing diesel with the diesel liquid nano-additives prepared in this invention, and the maximum energy-saving efficiency can reach more than 37%, indicating that the diesel liquid nano-additives prepared in this invention have significant energy-saving effects.

[0065] The above description is merely a preferred embodiment of the present invention, and therefore should not be construed as limiting the scope of the present invention. All equivalent changes and modifications made in accordance with the scope of the patent and the contents of the specification should still fall within the scope of the present invention.

Claims

1. A diesel liquid nano-additive, characterized in that: It is composed of the following components by mass percentage: 0.02-0.5% rare earth-based nanocatalyst, 52-67% cetane number improver, 1-5% smoke suppressant, 3-19% detergent-dispersant, 3-8% pour point depressant, 7-20% antioxidant, 5-13% lubricant, and surfactant. The mass ratio of surfactant to rare earth-based nanocatalyst is 2-10:

1. The antioxidant is 2,6-di-tert-butylphenol mixture. Rare earth-based nanocatalysts consist of a support and a catalytic metal supported on that support. The support is porous nano-CeO2 obtained by high-temperature calcination of a Ce-based metal-organic framework material. The porous nano-CeO2 has a particle size of 10-1000 nm and a specific surface area of ​​100-150 m². 2 g -1 The total pore volume is 0.1-0.5 cm³. 3 g -1 The catalytic metal is at least one selected from nickel, iron, manganese, zinc, copper, cobalt, gold, silver, and platinum, and the loading of the catalytic metal is 1-6 wt% of the support. The cetane number improver is at least one of isooctyl nitrate, dimethoxyethane, and ethyl lactate. The smoke suppressant is at least one of ferrocene, barium sulfate, tetrahydrofuran, and ethyl nitrate. The cleaning and dispersing agent is at least one of succinimide, tetrahydronaphthalene, and alkyl calcium salicylate. The pour point depressant is a polyethylene fumarate copolymer and / or an ethylene-vinyl acetate copolymer. The lubricant is a long-chain fatty acid methyl ester and / or ethylene glycol dinitrate.

2. The method for preparing the diesel liquid nano-additive according to claim 1, characterized in that: Includes the following steps: (1) Pour the rare earth-based nanocatalyst into the cetane number improver, then add the surfactant, ultrasonically vibrate for 0.5-2 h until completely dispersed, then stir and mix at a speed of 200-350 r / min for 30-50 min, and let stand naturally for 30-60 min. (2) Add lubricant, antioxidant, pour point depressant and detergent dispersant to the material obtained in step (1), and stir and mix at a speed of 120-250 r / min for 20-40 min; (3) Add smoke suppressant to the material obtained in step (2), stir and mix at a speed of 100-400 r / min for 60-90 min until completely dissolved, and then let it stand naturally for 1-2 h to obtain the diesel liquid nano additive.

3. The preparation method according to claim 2, characterized in that: The surfactant is at least one of hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, and sodium dodecyl sulfate.

Images