CN110747024A - Micro-emulsified diesel oil and preparation method thereof - Google Patents

Micro-emulsified diesel oil and preparation method thereof Download PDF

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Publication number
CN110747024A
CN110747024A CN201911215138.2A CN201911215138A CN110747024A CN 110747024 A CN110747024 A CN 110747024A CN 201911215138 A CN201911215138 A CN 201911215138A CN 110747024 A CN110747024 A CN 110747024A
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Prior art keywords
oil
stirring
parts
diesel oil
mass
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Inventor
彭均寿
王正富
薛卫平
陈爱军
彭均华
李恩发
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Chongqing Zhengtao New Energy Technology Co Ltd
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Chongqing Zhengtao New Energy Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Abstract

The invention discloses a micro-emulsified diesel oil and a preparation method thereof, wherein the micro-emulsified diesel oil is prepared from petrochemical diesel oil according to the mass part ratio
Figure DDA0002299294650000011
Figure DDA0002299294650000012
Composite surface active additive
Figure DDA0002299294650000013
Oil cleaning agent
Figure DDA0002299294650000014
Stabilizer
Figure DDA0002299294650000015
Light oil
Figure DDA0002299294650000016
Figure DDA0002299294650000017
Core additive
Figure DDA0002299294650000018
Diluent liquid
Figure DDA0002299294650000019
The composition is that firstly the petroleum diesel oil is treated
Figure DDA00022992946500000110
Adding the components into a stirring tank, and adding the composite surfactant
Figure DDA00022992946500000111
Stirring at 1200 rpmFor use, then the stabilizer is addedAdding into the diluent and stirring at constant speed
Figure DDA00022992946500000114
Adding core additive while stirring
Figure DDA00022992946500000115
Stirring for 15 min. Then adding the product to be used and stirring, and stirring by two-phase contact
Figure DDA00022992946500000116
Figure DDA00022992946500000117
Adding light oil after the oil becomes clear and transparent
Figure DDA00022992946500000120
Powder, core additiveContinuously stirring the components

Description

Micro-emulsified diesel oil and preparation method thereof
Technical Field
The invention relates to the technical field of vehicle fuel oil, in particular to micro-emulsified diesel oil.
Background
At present, energy conservation and pollution reduction of the consumption of finished petrochemical fuel oil are important subjects before people. With the shortage of energy, the combustion emission of various industrial machinery heavy vehicles and ships in operation becomes the largest pollution source, and in addition to the reduction of energy sources all over the world, China is the largest imported petroleum world in the world, and how to reduce the environmental pollution emission through cleaner energy sources has reached the ground to be solved. The pollution problem of conventional diesel oil combustion is solved, people replace and reduce the use of mineral diesel oil by researching and developing novel environment-friendly fuel, one of the difficult ways is to substitute part of mineral diesel oil by emulsified diesel oil, and the environment-friendly emulsified diesel oil is used as fuel and benefits the nation and the people for descendants to benefit.
The emulsified diesel oil is an energy-saving and environment-friendly technology which is added with water to the diesel oil to replace part of petroleum diesel oil for emulsification so as to completely burn the diesel oil. The technology of adding water into fuel oil has been proposed as early as many years ago. The technology can be used for enabling the fuel oil water emulsion to generate micro-explosion reaction during combustion. The secondary atomization of the fuel oil is caused, so that the combustion is more sufficient, the smoke intensity and the emission of harmful gas can be greatly reduced, and the fuel oil can replace part of petroleum diesel oil consumption, thereby realizing energy conservation and emission reduction.
Emulsified diesel oil is subjected to a plurality of large-scale diesel oil emulsification researches in the years, but due to various reasons, the technology is difficult to popularize, and a great progress is not made until 2010, the diesel oil microemulsion technology in China develops rapidly, a plurality of diesel oil emulsifier formulas are developed, but due to the following reasons, the technology cannot be popularized and enter the market:
1. the price of the emulsifier of the micro-emulsified diesel oil is high, and the raw materials in the formula are influenced.
2. The micro-emulsified diesel oil has poor stability and short shelf life when the additive is selected.
3. The blending process of the emulsified diesel oil is complex and unstable, and a special blending continuous production line is not available.
4. The national support for the policy of emulsified diesel oil is not strong.
On the other hand, although the micro-emulsified diesel oil in the prior art solves the problems of stability, power, storage life and the like, the micro-emulsified diesel oil can not be infinitely mixed with the existing mineral diesel oil in vehicle tests and practical use, oil-in-water emulsion is easily caused by a plurality of formulas when the micro-emulsified diesel oil meets water for the second time, and part of the micro-emulsified diesel oil still has the phenomenon of emulsion breaking, so that the oil supply of vehicles is insufficient, and the fire can be extinguished seriously and the oil circuit can be blocked. This poses a great risk of using the vehicle in actual use. Because the oil tank is cleaned before each new use, many vehicles do not choose to use the micro-emulsion water-added diesel oil.
Disclosure of Invention
The invention aims to provide a micro-emulsified diesel oil and a preparation method thereof, and aims to solve the problems explained in the background technology.
In order to achieve the aim, the invention provides a micro-emulsified diesel oil which is prepared by proportioning petrochemical diesel oil by mass
Figure BDA0002299294640000021
Composite surface active additive
Figure BDA0002299294640000022
Oil cleaning agent
Figure BDA0002299294640000023
Stabilizer
Figure BDA0002299294640000024
Light oil
Figure BDA0002299294640000025
Core additiveDiluent liquid
Figure BDA0002299294640000027
And (4) forming.
Wherein the diluent is soft water or methanol.
Wherein the composite surface active additive is prepared by mixing refined oleic acid in parts by mass
Figure BDA0002299294640000028
10-20 parts of naphthenic acid and 10 parts of biomass oil.
The oil cleaning agent comprises 8-12% of 30% of amine water, 40-50% of cyclohexylamine, 10-17% of potassium hydroxide and 28-36% of triethanolamine.
Wherein the stabilizer is prepared from n-iso-alcohol, n-butanol, tetrahydrofuran and n-hexanol in parts by mass
Figure BDA0002299294640000029
Figure BDA00022992946400000210
And (4) forming.
The light oil is prepared from No. 240 solvent oil, aviation kerosene, stone amine oil and methylal according to the mass part ratio of 50-70: 20-25: 6-18: 2 to 12.
The core additive is prepared from isoamyl nitrate, isooctyl nitrate, zinc peroxide and hydrazine hydrate according to a mass part ratio of 45-68: 14-70: 12-22: 3.2 to 5.4.
The invention also discloses a preparation method based on the micro-emulsified diesel oil, which comprises the following steps:
step 1: will be provided with
Figure BDA00022992946400000211
Adding petroleum diesel oil as base oil into stirring tank, adding composite surface active additive
Figure BDA00022992946400000212
Stirring the mixture in parts to form a mixed solution I, wherein the stirring speed is 1200r/h, and stirring the mixture
Figure BDA00022992946400000213
Standby;
step 2: stabilizing agent
Figure BDA00022992946400000214
Adding the mixture and clear oil agent 6-9
Figure BDA00022992946400000215
Stirring the diluted solution at a constant speedAdding core additive while stirring
Figure BDA00022992946400000217
The mixture is divided for 15min to form a mixed solution II;
and step 3: mixing the mixed solution I and the mixed solution II and stirring
Figure BDA00022992946400000218
Then add into
Figure BDA00022992946400000219
Light oil and
Figure BDA00022992946400000220
continuously stirring the core additive
Figure BDA00022992946400000221
Standing for 12h after the oil product is completely clear and transparent to obtain the finished oil.
Compared with the prior art, the invention has the beneficial effects that:
(1) the common petroleum diesel oil, the solvent light oil, the composite additive and the common soft water or methanol are mutually dissolved well at normal temperature and normal pressure, so that the particle size is in the range of 0.01-0.1 mm, and the color is clear and transparent microemulsion diesel oil.
(2) The micro-emulsified diesel oil has good stability, does not have the conditions of turbidity, floccule, suspended matter layering and the like within the temperature range of-10-65 ℃, does not break emulsion when used in a severe environment, does not melt when meeting water for the second time, and can reject excessive water outside, so that an oil tank does not need to be cleaned when the micro-emulsified diesel oil is used, and the micro-emulsified diesel oil can be infinitely mixed with common diesel oil. Vehicles have many options in use.
(3) The composite surfactant is adopted, and two kinds of ionic surfactants, namely refined oleic acid, naphthenic acid, cosurfactant n-iso-alcohol and n-butyl alcohol, are used to increase the water solubility of the emulsified diesel oil and achieve better emulsification effect. The water-soluble amount of the emulsified diesel oil is increased and the emulsifying effect is better by matching with a stabilizer containing normal-iso alcohol and normal-butyl alcohol components
(4) Aviation kerosene is used as a regulator, so that the power is high, the power is strong, the fuel is saved by 16%, the specific gravity is low, the lightning is high, and the safety of diesel oil in use is guaranteed.
(5) The stabilizer containing the normal-iso alcohol and normal-butanol components has good mutual fusibility, can be freely mixed and dissolved with the mineral diesel oil without limit, has excellent use effect and stability, and can ensure the oil product in use and transportation.
(6) The method has the advantages of good practicability, energy conservation of more than 8-20%, reduction of purification rate and improvement of 60%, adoption of a physical process for production, oil formation at normal temperature and normal pressure, no emission, easiness in purchase of raw materials, and suitability for popularization as high-quality oil.
(7) Because the composite surfactant is adopted, a proper amount of composite surfactant additive and stabilizer are added in the preparation method of the micro-emulsified diesel oil.
(8) The additive and the clear oil agent are actually subjected to comprehensive reaction to generate fatty acid soap and naphthenic acid soap, the good synergistic effect can ensure that added water can be completely and stably dispersed in an oil phase to form a water-in-oil type microemulsion, and simultaneously, due to the effect of the added triethanolamine, the microemulsion fatty acid diesel oil is clear and transparent and has a uniform system, so that when the emulsion diesel oil with the microemulsion particle size of 0.01-0.1 mm enters an engine, the emulsion diesel oil is homogeneous at each moment, ferrocene has the effects of eliminating smoke, reducing carbon deposition, saving energy and protecting environment, zinc peroxide is added for catalysis, and the effect of increasing the supply during secondary combustion is achieved. Tetrahydrofuran is added to improve the stability of the oil.
In summary, the following steps: the viscosity, the condensation point, the flash point and the cetane number of the micro-emulsified diesel oil formula product all meet the national VI index requirements of the automotive diesel oil. The raw and auxiliary materials are wide in source and low in price, the tail gas emission can meet the requirements of European No. 4 standard, and the oil saving rate of the vehicle micro-emulsified diesel oil reaches 32 percent. The fuel can be used as the fuel of a diesel automobile and the fuel of a diesel internal combustion engine of a ship, a tractor, agricultural machinery, a generator and the like, and the structure of the existing engine and the existing internal combustion engine does not need to be changed. The oil tank does not need to be cleaned before and after the addition, and the emulsified diesel oil is high in usability and can be popularized and used as commercial emulsified diesel oil.
Detailed Description
Please refer to table one:
Figure BDA0002299294640000041
watch 1
The micro-emulsified diesel oil in the embodiment 1 consists of 45 parts by mass of petrochemical diesel oil, 15 parts by mass of composite surface active additive, 7 parts by mass of clear oil agent, 2.8 parts by mass of stabilizer, 12 parts by mass of light oil, 1.2 parts by mass of core additive and 15 parts by mass of diluent. Wherein, the composite surface active additive consists of refined oleic acid 70, naphthenic acid 20 and biomass oil 10 in parts by mass; the clear oil agent consists of 30 mass percent of amine water 10, 40 mass percent of cyclohexylamine, 14 mass percent of potassium hydroxide and 36 mass percent of triethanolamine; the stabilizer is prepared from n-iso-alcohol, n-butanol, tetrahydrofuran and n-hexanol in a mass ratio of 82: 2: 12: 4, preparing a composition; the light oil is prepared from No. 240 solvent oil, aviation kerosene, stone amine oil and methylal according to the mass part ratio of 65: 25: 8: 2, preparing a composition; the core additive is prepared from isoamyl nitrate, ferrocene, isooctyl nitrate, zinc peroxide and hydrazine hydrate in a mass part ratio of 68: 0.6: 14: 12: 5.4; the diluent is methanol.
During preparation, 45 parts by mass of petroleum diesel oil serving as base oil is placed into a stirring tank, 15 parts by mass of composite surface active additive is added and stirred to form a mixed solution I, the stirring speed is 1200r/h, and the mixed solution I is stirred for 10min for later use; then adding 7 parts by mass of a stabilizer and an oil cleaning agent into 15 parts by mass of a diluent, stirring at a constant speed for 6min, and adding 0.6 part by weight of a core additive into the diluent until 15min to form a mixed solution II; and mixing and stirring the mixed solution I and the mixed solution II for 18min, adding 12 parts by mass of light oil and 0.6 part by mass of core additive, continuously stirring for 8min, and standing for 12h after the oil product is completely clear and transparent to obtain the finished oil.
The microemulsified diesel oil prepared by the components according to the mass portion ratio and the preparation method does not have demulsification phenomenon and oil-in-water emulsion in vehicle tests, has good intersolubility with the existing mineral diesel oil, can realize infinite miscibility, has smooth oil circuit in the use process of vehicles, supplies sufficient oil, has viscosity, condensation point, flash point and cetane number which all meet the national VI index requirements of the vehicle diesel oil, can meet the European No. 4 standard requirement of tail gas emission, and has the oil saving rate of 32 percent. Table two is a detection report made by a certain detection mechanism in Chongqing city to the microemulsified diesel in the embodiment, and the main performance indexes and detection results thereof please refer to table two:
Figure BDA0002299294640000051
watch two
The micro-emulsified diesel oil in the embodiment 2 consists of petrochemical diesel oil 51, a composite surface active additive 13, a clear oil agent 9, a stabilizer 2.4, light oil 10, a core additive 0.6 and a diluent 13 according to the mass part ratio. Wherein, the composite surface active additive consists of refined oleic acid 75, naphthenic acid 15 and biomass oil 10 in parts by mass; the clear oil agent consists of 30 mass percent of amine water 12, 50 mass percent of cyclohexylamine, 10 mass percent of potassium hydroxide and 28 mass percent of triethanolamine; the stabilizer is prepared from n-iso-alcohol, n-butanol, tetrahydrofuran and n-hexanol in a mass ratio of 4: 75: 13: 8, preparing a mixture; the light oil is prepared from No. 240 solvent oil, aviation kerosene, stone amine oil and methylal according to the mass part ratio of 50: 20: 18: 12; the core additive is prepared from isoamyl nitrate, ferrocene, isooctyl nitrate, zinc peroxide and hydrazine hydrate according to the mass part ratio of 12: 0.5: 65: 18: 4.5; the diluent is methanol.
During preparation, 51 parts by mass of petroleum diesel oil serving as base oil is placed into a stirring tank, 14 parts by mass of composite surface active additive is added and stirred to form a mixed solution I, the stirring speed is 1200r/h, and the mixed solution I is stirred for 12min for later use; then adding 2.4 parts by mass of stabilizer and 9 parts by mass of clear oil agent into 13 parts by mass of diluent, stirring at a constant speed for 8min, and adding 0.3 part by weight of core additive into the diluent until 15min to form a mixed solution II; and mixing and stirring the mixed solution I and the mixed solution II for 20min, adding 10 parts by mass of light oil and 0.3 part by mass of core additive, continuously stirring for 10min, and standing for 12h after the oil product is completely clear and transparent to obtain the finished oil.
The microemulsified diesel oil prepared by the components according to the mass portion ratio and the preparation method does not have demulsification phenomenon and oil-in-water emulsion in vehicle tests, has good intersolubility with the existing mineral diesel oil, can realize infinite miscibility, has smooth oil circuit in the use process of vehicles, supplies sufficient oil, has viscosity, condensation point, flash point and cetane number which all meet the national VI index requirements of the vehicle diesel oil, can meet the European No. 4 standard requirement of tail gas emission, and has the oil saving rate of 32 percent. The second table shows a detection report made by a certain detection mechanism in Chongqing city on the microemulsified diesel in the embodiment, and the main performance indexes and detection results thereof are shown in the third table:
Figure BDA0002299294640000061
watch III
The micro-emulsified diesel oil in the embodiment 3 consists of 64 parts by mass of petrochemical diesel oil, 11 parts by mass of composite surface active additive, 6 parts by mass of clear oil agent, 2.2 parts by mass of stabilizer, 6 parts by mass of light oil, 0.8 part by mass of core additive and 10 parts by mass of diluent. Wherein, the composite surface active additive consists of 80 parts by mass of refined oleic acid, 10 parts by mass of naphthenic acid and 10 parts by mass of biomass oil; the clear oil agent consists of 30 mass percent of aqueous amine 8, cyclohexylamine 45, potassium hydroxide 17 and triethanolamine 30; the stabilizer is prepared from n-iso-alcohol, n-butanol, tetrahydrofuran and n-hexanol in a mass ratio of 8: 8: 15: 69; the light oil is prepared from No. 240 solvent oil, aviation kerosene, stone amine oil and methylal according to the mass part ratio of 70: 20: 6: 4, preparing a composition; the core additive is prepared from isoamyl nitrate, ferrocene, isooctyl nitrate, zinc peroxide and hydrazine hydrate according to the mass part ratio of 45: 0.3: 70: 22: 3.2; the diluent is methanol.
During preparation, petroleum diesel oil with the mass ratio of 64 is used as base oil and is placed into a stirring tank, composite surface active additive with the mass ratio of 11 is added and stirred to form mixed solution I, the stirring speed is 1200r/h, and the mixed solution I is stirred for 10min for standby; then adding 6 parts by mass of a stabilizer and an oil cleaning agent into 10 parts by mass of a diluent, stirring at a constant speed for 6min, and adding 0.4 part by weight of a core additive into the diluent until 15min to form a mixed solution II; and mixing and stirring the mixed solution I and the mixed solution II for 18min, adding 6 parts by mass of light oil and 0.4 part by mass of core additive, continuously stirring for 8min, and standing for 12h after the oil product is completely clear and transparent to obtain the finished oil.
The microemulsified diesel oil prepared by the components according to the mass portion ratio and the preparation method does not have demulsification phenomenon and oil-in-water emulsion in vehicle tests, has good intersolubility with the existing mineral diesel oil, can realize infinite miscibility, has smooth oil circuit in the use process of vehicles, supplies sufficient oil, has viscosity, condensation point, flash point and cetane number which all meet the national VI index requirements of the vehicle diesel oil, can meet the European No. 4 standard requirement of tail gas emission, and has the oil saving rate of 32 percent. Table three is a detection report made by a certain detection mechanism in chongqing city on the microemulsified diesel in the embodiment, and the main performance indexes and detection results thereof are shown in table four:
Figure BDA0002299294640000071
watch four
It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should also be understood that various alterations, modifications and/or variations can be made to the present invention by those skilled in the art after reading the technical content of the present invention, and all such equivalents fall within the protective scope defined by the claims of the present application.

Claims (8)

1. A micro-emulsified diesel oil is characterized in that: 45-64 parts of petroleum diesel, 11-15 parts of composite surface active additive and clear oil agent
Figure FDA0002299294630000011
Stabilizer
Figure FDA0002299294630000012
Light oil
Figure FDA0002299294630000013
Core additiveDiluent liquid
Figure FDA0002299294630000015
And (4) forming.
2. A microemulsified diesel as claimed in claim 1, wherein said diluent is soft water or methanol.
3. The microemulsified diesel of claim 1, wherein said composite surface active additive is prepared from essential oleic acid by weight10-20 parts of naphthenic acid and 10 parts of biomass oil.
4. A micro-emulsified diesel oil as set forth in claim 1, wherein the oil cleaning agent is composed of 30% by mass of 8-12% of amine water, 40-50% of cyclohexylamine, 10-17% of potassium hydroxide and 28-36% of triethanolamine.
5. A microemulsified diesel as claimed in claim 1, wherein the stabilizer is composed of n-iso-alcohol, n-butanol, tetrahydrofuran and n-hexanol in parts by mass
Figure FDA0002299294630000017
And (4) forming.
6. A microemulsion diesel oil as claimed in claim 1, wherein the light oil is prepared from No. 240 solvent oil, aviation kerosene, stone amine oil and methylal according to the mass part ratio of 50-70: 20-25: 6-18: 2 to 12.
7. A microemulsified diesel oil according to claim 1, wherein the core additive is prepared from isoamyl nitrate, ferrocene, isooctyl nitrate, zinc peroxide and hydrazine hydrate in a mass ratio of 45-68: 0.3-0.6: 14-70: 12-22: 3.2 to 5.4.
8. A method for preparing a microemulsified diesel as claimed in any one of claims 1-7, characterized by comprising the steps of:
step 1: will be provided with
Figure FDA0002299294630000018
Adding petroleum diesel oil as base oil into stirring tank, adding composite surface active additive
Figure FDA0002299294630000019
Stirring the mixture in parts to form a mixed solution I, wherein the stirring speed is 1200r/h, and stirring the mixture
Figure FDA00022992946300000110
Standby;
step 2: stabilizing agent
Figure FDA00022992946300000111
Adding 6-9 parts of the diluent and 6-9 parts of the clear oil agent into 10-15 parts of the diluent, stirring at a constant speed for 6-8 min, and adding 0.6-1.2 parts of the core additive into the mixture until 15min to form a mixed solution II;
and step 3: and mixing and stirring the mixed solution I and the mixed solution II for 18-20 min, adding 6-12 parts of light oil and 0.6-1.2 parts of core additive, continuously stirring for 8-10 min, and standing for 12h after the oil product is completely clear and transparent to obtain the finished oil.
CN201911215138.2A 2019-12-02 2019-12-02 Micro-emulsified diesel oil and preparation method thereof Pending CN110747024A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101058747A (en) * 2007-06-21 2007-10-24 刘同元 Emulsification diesel fuel additive, emulsification diesel fuel using the same and preparation method thereof
CN101514299A (en) * 2009-03-03 2009-08-26 陈庆军 Compound diesel
CN103642542A (en) * 2013-12-25 2014-03-19 济南开发区星火科学技术研究院 Methanol diesel oil
WO2017075744A1 (en) * 2015-11-02 2017-05-11 深圳市广昌达石油添加剂有限公司 Compound additive for preventing spontaneous combustion of diesel antiwear agent

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101058747A (en) * 2007-06-21 2007-10-24 刘同元 Emulsification diesel fuel additive, emulsification diesel fuel using the same and preparation method thereof
CN101514299A (en) * 2009-03-03 2009-08-26 陈庆军 Compound diesel
CN103642542A (en) * 2013-12-25 2014-03-19 济南开发区星火科学技术研究院 Methanol diesel oil
WO2017075744A1 (en) * 2015-11-02 2017-05-11 深圳市广昌达石油添加剂有限公司 Compound additive for preventing spontaneous combustion of diesel antiwear agent

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