A composite additive for light hydrocarbon liquid fuel and its preparation method and application

Abstract

The present invention belongs to the technical field of light hydrocarbon liquid fuel additives, and specifically discloses a composite additive for light hydrocarbon liquid fuel, a preparation method thereof and an application thereof. The composite additive comprises the following components in parts by weight: 12-18 parts of explosion-proof agent, 6-9 parts of vegetable oil, 2-4 parts of catalyst, 4-8 parts of cosolvent, 3-5 parts of emulsifier, 1.2-2.5 parts of antioxidant, and 22-27 parts of solvent oil; the explosion-proof agent is a compound of ethyl tert-butyl ether and carbonate; the catalyst is a modified graphene / nano titanium oxide composite. The additive provided in this application can modify low-cost low-carbon liquid light hydrocarbons, increase the octane number of liquid light hydrocarbons, improve their combustion performance, and reduce costs and environmental pollution.

Description

Technical Field

[0001] The invention belongs to the technical field of light hydrocarbon liquid fuel additives, and in particular relates to a composite additive for light hydrocarbon liquid fuel and a preparation method and application thereof. Background Art

[0002] In recent years, with the continuous depletion of oil resources, the scientific and full utilization of light hydrocarbons, how to transform low-cost low-carbon light hydrocarbons into high value-added products has always been a difficult problem that the petrochemical industry needs to solve urgently. Liquid light hydrocarbons usually refer to a mixture of alkanes or monoolefins mainly based on C5. They are generally in a liquid state at normal temperature and pressure and are by-products (condensate oil) in the process of oil extraction and processing. The utilization rate of liquid light hydrocarbons is very low. Most of the light hydrocarbons are converted into gaseous state to improve their utilization rate, but the saturated vapor pressure of liquid light hydrocarbons is high, and the octane number is low and unstable. If it is added directly without scientific modification, the octane number of the fuel gas will be reduced, the combustion efficiency will be reduced, and there will be certain safety hazards.

[0003] Patent CN115125040A discloses a pentane-based cutting fluid additive and its preparation method and application, which is used to add to liquid light hydrocarbons with pentane as the main component. However, the anti-knock property of liquid light hydrocarbons is relatively poor, and anti-knock agents can increase the octane number to prevent or reduce the high molecular polymers produced by the knock when the light hydrocarbons are burned. Among them, alkyl lead has become a widely used anti-knock agent, such as tetramethyl lead, tetraethyl lead and their mixtures, but this type of lead-containing anti-knock agent is toxic and causes environmental pollution. Later, the addition of ethers such as methyl tert-butyl ether can also effectively improve the octane number, but there are the disadvantages of large addition amount, high cost and anesthetic effect on operators. Therefore, the development of a new, efficient, environmentally friendly and low-cost liquid light hydrocarbon additive is still an urgent problem to be solved. Summary of the invention

[0004] The purpose of the present invention is to overcome the defects and shortcomings of the prior art, provide a composite additive for light hydrocarbon liquid fuel and its preparation method and application, improve the octane number of light hydrocarbon fuel, significantly improve the combustion performance of the fuel, and use less additives and do not contain lead, which significantly reduces costs and pollution to the environment.

[0005] The primary purpose of the present application is to provide a composite additive for light hydrocarbon liquid fuel, comprising the following components in parts by weight: 11.0-18.0 parts of explosion-proof agent, 6.0-9.0 parts of vegetable oil, 1.5-4.0 parts of catalyst, 4.0-8.0 parts of cosolvent, 3.0-5.0 parts of emulsifier, 1.2-2.5 parts of antioxidant, and 22.0-27.0 parts of solvent oil;

[0006] The explosion-proof agent is a compound of ethyl tert-butyl ether (ETBE) and carbonates; and the catalyst is a modified graphene-nano titanium oxide composite.

[0007] Preferably, the carbonate is selected from any one or more of propylene carbonate (PC), ethylene carbonate (EC), and chloroethylene carbonate (CEC).

[0008] Further preferably, the mixing ratio of carbonates to ethyl tert-butyl ether (ETBE) in the explosion-proof agent is 1 to 4:10 in parts by weight.

[0009] Preferably, the vegetable oil is one or more of linseed oil, soybean oil, castor oil, palm oil, etc. The unsaturated fatty acids in the vegetable oil can be decomposed into ions from long-chain molecules after ultrasonic treatment, and are further wrapped by solvent oil molecules and co-solvent alcohol molecules to participate in co-combustion, thereby increasing the combustion calorific value.

[0010] Preferably, the catalyst preparation step comprises: dispersing graphene oxide in ethanol by ultrasonication to obtain a graphene oxide dispersion, then adding n-butyl titanate, stirring, adding water and triethanolamine, subjecting the mixed dispersion to a hydrothermal reaction, and washing and drying the obtained reactant to obtain

[0011] Preferably, the mass ratio of graphene oxide to n-butyl titanate in the preparation of the composite catalyst is 1:50 to 1:420, and the hydrothermal reaction conditions are 150 to 180° C. for 12 to 18 hours.

[0012] Preferably, the emulsifier is one of Span 60 and Span 80.

[0013] Preferably, the co-solvent is tert-butyl alcohol, isopropyl alcohol, acetone or a mixture thereof.

[0014] Preferably, the antioxidant is a mixture of one or more of 2,6-di-tert-butyl-p-cresol (BHT), 2,6-di-tert-butylphenol and N,N-di-sec-butylhydroquinone.

[0015] Preferably, the solvent oil is naphtha or kerosene.

[0016] Light hydrocarbon fuel is a complex mixture, and its quality indicators such as octane number, vapor pressure, flash point, etc. are not additive. When the additive prepared in this application is added to liquid light hydrocarbons, the vapor pressure of each component in the additive is very low, which affects the vapor pressure of each component in the liquid light hydrocarbons; the additive is a mixture of a multi-component system, and each component can be miscible with the liquid light hydrocarbons in any proportion; it can cause the octane number, saturated vapor pressure and other indicators of the liquid light hydrocarbons to change significantly, and can make the liquid light hydrocarbons become qualified fuel (gas) and improve combustion efficiency. This result is not the simple addition of the performance of each component, but the result of synergy.

[0017] The second object of the present application is to provide a method for preparing a composite additive for light hydrocarbon liquid fuel, comprising the following steps:

[0018] S1, firstly, vegetable oil, explosion-proof agent, solvent oil and part of co-solvent are mixed, then stirred at a constant temperature, and cooled to obtain mixture I;

[0019] S2, mixing and stirring the remaining co-solvent, catalyst and antioxidant to obtain a mixture II;

[0020] S3, adding an emulsifier to the mixture I, then dropping the mixture II into the mixture I, and stirring evenly.

[0021] The third object of the present application is to provide an application of the composite additive prepared by the above method in improving the octane number and combustion performance of light hydrocarbon liquid fuel, wherein the weight ratio of the additive to the light hydrocarbon is 3 to 10:100.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] The present invention provides a composite additive for light hydrocarbon liquid fuel, a preparation method and application thereof. By adjusting and modifying the components of the composite additive, the cost can be reduced while the quality can be guaranteed, the octane number of the fuel (gas) is effectively increased, the combustion performance of liquid light hydrocarbons is improved, and the cost and pollution to the environment are reduced, thereby achieving both economic and social benefits. DETAILED DESCRIPTION

[0024] The specific embodiments of the present invention below will provide a detailed and comprehensive description of the technical solutions of the present invention. It should be noted that the embodiments provided represent only a part of the present invention, not all of it. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0025] Unless otherwise specified, the test methods used in the examples of the present invention are all conventional methods; the materials, reagents, etc. used are reagents and materials that can be obtained from commercial channels, unless otherwise specified, and the commercially available raw materials are filtered to remove impurities such as insoluble matter. Ethyl tert-butyl ether was purchased from Guangdong Yuantai Chemical Co., Ltd., propylene carbonate was purchased from Shandong Jinhai Chemical Technology Co., Ltd., ethylene carbonate was purchased from Shandong Pulaihua Chemical Co., Ltd., and ethylene chlorocarbonate was purchased from Jinan Mingshuo Chemical Co., Ltd.

[0026] The catalyst used in the embodiments and comparative examples of the present invention is a modified graphene / nano-titanium oxide composite prepared under the same conditions, and its preparation steps include: dispersing graphite oxide in ethanol and ultrasonically obtaining a graphene oxide dispersion, then adding n-butyl titanate, stirring, adding water and triethanolamine, subjecting the mixed dispersion to a hydrothermal reaction, and washing the obtained reaction product and drying it. The specific experimental operation is as follows: (1) 50 mg of graphene oxide is dispersed in 50 mL of anhydrous ethanol, and ultrasonicated for 45 min to obtain a graphene oxide ethanol dispersion; (2) n-butyl titanate is added to the graphene oxide dispersion, the mass ratio of graphene oxide to n-butyl titanate is 1:200, and stirred for 60 min. 1 mL of deionized water and 2% of the total mass (graphene oxide and n-butyl titanate) of triethanolamine are added, and stirring is continued for 60 min; (3) The mixed solution is transferred to a reactor and hydrothermally reacted at 180°C for 18 h; 4) The reaction product is washed with anhydrous ethanol and deionized water in turn, and dried at 80°C in a vacuum.

[0027] Example 1

[0028] A composite additive for light hydrocarbon liquid fuel comprises the following components in parts by weight: 12.8 parts of ETBE, 3.2 parts of PC, 7.5 parts of castor oil, 2.5 parts of modified graphene / nano titanium oxide composite, 3.5 parts of tert-butyl alcohol, 3.5 parts of acetone, 4.0 parts of Span 80, 2.0 parts of BHT and 25.0 parts of kerosene.

[0029] The preparation method of the composite additive comprises the following steps:

[0030] (1) firstly, the castor oil, ETBE, PC, kerosene and 1 / 2 amount of the co-solvent (a mixture of tert-butyl alcohol and acetone) in the above-mentioned weight parts are mixed, and then placed in a constant temperature water bath at 30° C. and stirred at 500 rpm for 3 h, and then cooled to obtain a first mixture;

[0031] (2) then mixing and stirring the remaining amount of the co-solvent, the modified graphene / nano-titanium oxide composite and BHT to obtain a second mixture;

[0032] (3) Span 80 was added to the first mixture, and then the second mixture was added dropwise to the first mixture, and magnetic stirring was performed for 4 hours to obtain an additive.

[0033] Example 2

[0034] A composite additive for light hydrocarbon liquid fuel comprises the following components in parts by weight: 10.0 parts of ETBE, 1.0 parts of PC, 9.0 parts of castor oil, 3.0 parts of modified graphene / nano titanium oxide composite, 2.0 parts of tert-butyl alcohol, 2.0 parts of acetone, 3.0 parts of Span 80, 1.2 parts of BHT and 27.0 parts of kerosene.

[0035] The preparation method of the composite additive is the same as that of Example 1.

[0036] Example 3

[0037] A composite additive for light hydrocarbon liquid fuel comprises the following components in parts by weight: 10.0 parts of ETBE, 4.0 parts of PC, 8.0 parts of castor oil, 1.5 parts of modified graphene / nano titanium oxide composite, 3.0 parts of tert-butyl alcohol, 3.0 parts of acetone, 4.0 parts of Span 80, 1.8 parts of BHT and 23.0 parts of kerosene.

[0038] The preparation method of the composite additive is the same as that of Example 1.

[0039] Example 4

[0040] A composite additive for light hydrocarbon liquid fuel comprises the following components in parts by weight: 12.8 parts of ETBE, 3.2 parts of EC, 6.0 parts of castor oil, 2.0 parts of modified graphene / nano titanium oxide composite, 5.0 parts of isopropanol, 3.5 parts of Span 80, 1.0 part of BHT, 1.0 part of 2,6-di-tert-butylphenol, and 24.0 parts of kerosene.

[0041] The preparation method of the composite additive comprises the following steps:

[0042] (1) firstly, the castor oil, ETBE, EC, kerosene and 1 / 2 amount of isopropanol in the above-mentioned parts by weight are mixed, and then placed in a constant temperature water bath at 30° C. and stirred at 500 rpm for 3 h, and then cooled to obtain a first mixture;

[0043] (2) then mixing and stirring the remaining amount of isopropanol, the modified graphene / nano-titanium oxide composite, BHT, and 2,6-di-tert-butylphenol to obtain a second mixture;

[0044] (3) Span 80 was added to the first mixture, and then the second mixture was added dropwise to the first mixture, and magnetic stirring was performed for 4 hours to obtain an additive.

[0045] Example 5

[0046] A composite additive for light hydrocarbon liquid fuel comprises the following components in parts by weight: 15.0 parts of ETBE, 3.0 parts of EC, 7.5 parts of castor oil, 4.0 parts of modified graphene / nano titanium oxide composite, 4.0 parts of isopropanol, 4.0 parts of acetone, 5.0 parts of Span 80, 2.5 parts of N,N-di-sec-butylhydroquinone, and 26.0 parts of kerosene.

[0047] The preparation method of the composite additive comprises the following steps:

[0048] (1) firstly, the castor oil, ETBE, EC, kerosene and 1 / 2 amount of the co-solvent (mixture of isopropanol and acetone) in the above-mentioned weight parts are mixed, and then placed in a constant temperature water bath at 30° C. and stirred at 500 rpm for 3 h, and then cooled to obtain a first mixture;

[0049] (2) then mixing and stirring the remaining amount of the co-solvent, the modified graphene / nano-titanium oxide composite and N,N-di-sec-butylhydroquinone to obtain a second mixture;

[0050] (3) Span 80 was added to the first mixture, and then the second mixture was added dropwise to the first mixture, and magnetic stirring was performed for 4 hours to obtain an additive.

[0051] Comparative Example 1

[0052] A composite additive for light hydrocarbon liquid fuel comprises the following components in parts by weight: 16.0 parts of ETBE, 7.5 parts of castor oil, 2.5 parts of modified graphene / nano titanium oxide composite, 3.5 parts of tert-butyl alcohol, 3.5 parts of acetone, 4.0 parts of Span 80, 2.0 parts of BHT and 25.0 parts of kerosene.

[0053] The preparation method of the composite additive is the same as that of Example 1.

[0054] Comparative Example 2

[0055] A composite additive for light hydrocarbon liquid fuel comprises the following components in parts by weight: 16.0 parts of PC, 7.5 parts of castor oil, 2.5 parts of modified graphene / nano titanium oxide composite, 3.5 parts of tert-butyl alcohol, 3.5 parts of acetone, 4.0 parts of Span 80, 2.0 parts of BHT and 25.0 parts of kerosene.

[0056] The preparation method of the composite additive is the same as that of Example 1.

[0057] Comparative Example 3

[0058] A composite additive for light hydrocarbon liquid fuel comprises the following components in parts by weight: 12.8 parts of MTBE (methyl tert-butyl ether), 3.2 parts of PC, 7.5 parts of castor oil, 2.5 parts of modified graphene / nano titanium oxide composite, 3.5 parts of tert-butyl alcohol, 3.5 parts of acetone, 4.0 parts of Span 80, 2.0 parts of BHT and 25.0 parts of kerosene.

[0059] The preparation method of the composite additive is the same as that of Example 1.

[0060] Comparative Example 4

[0061] A composite additive for light hydrocarbon liquid fuel comprises the following components in parts by weight: 12.8 parts of ETBE, 3.2 parts of PC, 7.5 parts of castor oil, 2.5 parts of a graphene / nano-titanium oxide mixture, 3.5 parts of tert-butyl alcohol, 3.5 parts of acetone, 4.0 parts of Span 80, 2.0 parts of BHT, and 25.0 parts of kerosene; wherein the graphene-nano-titanium oxide mixture is prepared by mixing 50 mg of graphene oxide and 2.35 g of nano-titanium dioxide uniformly and weighing the components by weight.

[0062] The preparation method of the composite additive is the same as that of Example 1.

[0063] Comparative Example 5

[0064] A composite additive for light hydrocarbon liquid fuel comprises the following components in parts by weight: 12.8 parts of ETBE, 3.2 parts of PC, 7.5 parts of castor oil, 2.5 parts of modified graphene / nano titanium oxide composite, 3.5 parts of tert-butyl alcohol, 3.5 parts of acetone, 4.0 parts of Span 80, 2.0 parts of BHT and 25.0 parts of kerosene.

[0065] The preparation method of the composite additive is to weigh various substances according to the formula amount, put them into a container and stir them evenly.

[0066] Quality indicator testing and application performance

[0067] 1. The composite additives prepared in the examples and comparative examples of the present application were added to liquid light hydrocarbons (Ningxia Shenrui condensate oil raw material octane number RON is 75) at a weight ratio of 8:100, and after being stirred evenly, the quality indicators were tested after standing for 12 hours. The results are shown in Table 1.

[0068] As can be seen from Table 1, the composite additive prepared by the present invention can be added to liquid light hydrocarbon fuel to prepare light hydrocarbon modified fuel (gas), which improves the octane number of liquid light hydrocarbon (from 75 of the raw material to more than 93) and has low corrosion to metals.

[0069] Compared to comparative examples 1-3, in the embodiment of the present invention, explosion-proof agent adopts ethyl tert-butyl ether (ETBE) and carbonates composite use, due to the presence of double bonds, can act with peroxide under high temperature and high pressure conditions, thereby effectively reducing peroxide, reducing the concentration of peroxide in flame pre-reaction, and improving the anti-explosion performance of fuel. Ethyl tert-butyl ether (ETBE) is generally prepared by mixing ethanol with isobutylene. In a specific embodiment of the present invention, ETBE and carbonates are composited and used, and carbonates have the effect of synergizing ETBE to improve octane number. Meanwhile, ETBE can also be used as a cosolvent, and its boiling point is higher, and it does not generate azeotropic compounds when mixed with liquid hydrocarbons, so that gas resistance can be reduced, and evaporation loss can be reduced again. Composite explosion-proof agent can not only significantly improve the octane number of light hydrocarbon liquid fuel, but also its economy and safety are better than adding MTBE.

[0070]

[0071] Compared with Comparative Example 4, the modified graphene / nano-titanium oxide composite catalyst of the present invention can be quickly and evenly dispersed in other components. When added to liquid light hydrocarbon fuel, it can be dispersed more evenly in the fuel, weaken the force between fuel molecules, effectively decompose the unequal agglomeration structure between fuel molecules, and form gasified mist particles centered on dispersed nanoparticles, thereby increasing the combustion efficiency and making the combustion more complete. At the same time, the modified composite catalyst of the present invention increases the interface of the fuel system, increases the contact area with the air, and effectively improves the combustion speed.

[0072] Obviously, the above embodiments of the present invention are only examples for clearly illustrating the technical solution of the present invention, and are not intended to limit the specific implementation methods of the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the claims of the present invention shall be included in the protection scope of the claims of the present invention.

Claims

1. A composite additive for light hydrocarbon liquid fuel, characterized in that: The invention comprises the following components in parts by weight: 11.0-18.0 parts of explosion-proof agent, 6.0-9.0 parts of vegetable oil, 1.5-4.0 parts of catalyst, 4.0-8.0 parts of cosolvent, 3.0-5.0 parts of emulsifier, 1.2-2.5 parts of antioxidant and 22.0-27.0 parts of solvent oil; wherein the explosion-proof agent is a compound of ethyl tert-butyl ether and carbonate; the catalyst is a modified graphene-nano titanium oxide composite; the catalyst is a composite of graphene oxide Graphene is dispersed in ethanol by ultrasound to obtain a graphene oxide dispersion, then n-butyl titanate is added, water and triethanolamine are added after stirring, the mixed dispersion is subjected to a hydrothermal reaction, and the obtained reactant is washed and dried to obtain; the mass ratio of the graphene oxide to n-butyl titanate is 1:50 to 1:420, and the hydrothermal reaction condition is 150 to 180° C. for 12 to 18 hours; the mixing ratio of carbonates to ethyl tert-butyl ether in the explosion-proof agent is 1 to 3:4 in parts by weight.

2. The additive according to claim 1, characterized in that The carbonates are selected from any one or more of propylene carbonate, ethylene carbonate, and chloroethylene carbonate.

3. The additive according to claim 1, characterized in that The vegetable oil is one of linseed oil, soybean oil, castor oil and palm oil.

4. The additive according to claim 1, characterized in that The co-solvent is one of tert-butyl alcohol, isopropyl alcohol, acetone or a mixture thereof.

5. The additive according to claim 1, characterized in that The antioxidant is a mixture of one or more of 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol and N,N-di-sec-butylhydroquinone.

6. The additive according to claim 1, characterized in that The solvent oil is naphtha or kerosene.

7. The method for preparing a composite additive for light hydrocarbon liquid fuel according to any one of claims 1 to 6, characterized in that: The steps include: S1, firstly, vegetable oil, explosion-proof agent, solvent oil and part of co-solvent are mixed, then stirred at a constant temperature, and cooled to obtain mixture I; S2, mixing and stirring the remaining co-solvent, catalyst and antioxidant to obtain a mixture II; S3, adding an emulsifier to the mixture I, and then slowly dropping the mixture II into the mixture I, and stirring evenly.

8. The use of the composite additive for light hydrocarbon liquid fuel according to claim 1 in improving the octane number and combustion performance of light hydrocarbon liquid fuel, characterized in that: The weight ratio of the additive added to the light hydrocarbon liquid fuel is 3 to 10:100.

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