CN102876405A - Preparation methods of diesel microemulsion and micro-emulsified diesel oil - Google Patents
Preparation methods of diesel microemulsion and micro-emulsified diesel oil Download PDFInfo
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Abstract
The invention relates to preparation methods of a diesel microemulsion and micro-emulsified diesel oil. The optimum composition proportion (by mass percent) is: 84.4% of diesel oil, 5.0% of a compounded emulsifier, 0.2% of auxiliaries, and 10.4% of water. The microemulsion prepared in the invention does not contain metal ions, halogen, sulfur and other substances detrimental to equipment and the environment. Belonging to oxygenated chemicals, the microemulsion contributes to complete combustion of micro-emulsified diesel oil, thus improving the combustion efficiency. With the advantages of simple preparation and low cost, the microemulsion can be stored for a long time, is miscible with pure diesel oil within certain range, and can significantly reduce the discharge of solid particles, CO, NOx and other tail gases, thus being conducive to environmental protection.
Description
[technical field]
The present invention relates to the diesel oil microemulsion technical field, specifically, is the preparation method of a kind of diesel oil microemulsion and micro emulsion diesel fuel.
[background technology]
Along with the fast development of industry, agricultural and transportation etc., the environmental pollution that the shortage of fossil energy and burning thereof bring is day by day serious, and how efficiently utilizing fossil energy and reducing pollution emissions just becomes the matter of utmost importance of country and social concerns.The fuel water technology begins to be subject to the extensive concern of various countries from last century, early stage fuel water technical study mainly concentrates on the fuel emulsification aspect, but emulsified fuel has following drawback: (1) is unstable, can be elongated with envrionment conditions change and storage period, the wild effects such as oily water separation, breakdown of emulsion occur; (2) preparation is complicated, needs high-power emulsifier unit, and energy consumption is larger; (3) be creamy white in appearance, differ greatly with diesel oil, the user is difficult for accepting.Above-mentioned drawback has restricted its popularization and use.The eighties in 20th century, the research of micro-emulsified fuel makes the fuel water technology enter into a new developmental stage.Microemulsion fuel is a kind of thermodynamic stable system, possesses following advantage: (1) preparation is simple, slightly rocks and can obtain, and also can utilize ultra-sonic dispersion, shortens preparation time; (2) good stability can be placed for a long time; (3) outward appearance and modest viscosity differ with pure fuel oil and not to be very large; (4) reduction of discharging and energy-conservation, soot and NO
xDeng the Reducing exhaust emission of tail gas, efficiency of combustion improves.
At present, the general good stability of domestic micro-emulsified fuel, good with pure fuel oil compatibility, but the research of domestic fuel oil microemulsified has the following disadvantages:
(1) metal ion in the microemulsion, halogen, the element such as sulphur, phosphorus and corrosives, after adding fuel oil, can cause that mechanical impurity and other impurity increase in the diesel oil, engine high pressure fuel injection pump plunger, delivery valve, oil thrower couple etc. will the abnormal in early stage wearing and tearing, and easily in exhaust treatment system catalyst surface form sluggish material, make poisoning of catalyst, thus active unfavorable to catalyzer.Micro-emulsified fuel good stability such as China Patent Publication No. CN87104283A, CN1146482A, CN1718693A, CN1896194A, CN101445745A, CN1718682A, CN1422934A, CN1130672A and application number 201110021530.0 preparations, storage time is long, but in fuel oil, the metal ions such as potassium, sodium have been introduced, or the elements such as sulphur, phosphorus, or halogen, corrosives.Patent CN101629110A discloses a kind of theamin sex change sugar and has been the high water transparent microemulsified nanometer particle size fuel of low agent of heat value agent, can stablize more than 1 year, and have novelty aspect the sugared alternative fuel, but introduce metal-salt in the water-splitting microemulsion.China Patent Publication No. CN101649228A, application number 201010250069.1, the disclosed micro emulsion diesel fuel of China Patent Publication No. CN101126038A, the microemulsion consumption is few, and watering quantity is many, but microemulsion metal ion and halogen.China's application number 200910231033.6, the disclosed micro-emulsification fuel oil of China Patent Publication No. CN101348739A, good stability, microemulsion can be applicable to diesel oil and gasoline, but has introduced metal ion, element sulphur, halogen and the corrosivess such as potassium, sodium.
(2) the microemulsion consumption is many, and water mixing is few, causes the microemulsion fuel cost higher, the application of unfavorable micro-emulsion technology and popularization.Such as China Patent Publication No. CN1422935A, CN1410514A, the disclosed micro-emulsified fuel of CN1239731A, microemulsion mainly is comprised of lipid acid, amine, alcohols and nonionogenic tenside, do not introduce metal ion, halogen and element sulphur, but the microemulsion consumption is many, water mixing is few, such as amount of water 13% among the China Patent Publication No. CN1422935A, the total consumption of oleic acid and thanomin reaches 12%.Chinese patent application numbers 201010110763.3 relates to a kind of micro-emulsion clean fuel, and this is invented except flash-point, and all the other performances and international diesel oil are very approaching, technique is simple, and cost is low, and noxious gas emission reduces, but the microemulsion consumption is more than 8%, and water mixing only has 6～10%.Chinese patent application numbers 201010186851.1 relates to a kind of high flash point clean energy-saving micro emulsion diesel fuel and compound method thereof, and flash-point is high, is 63～78 ℃, and dynamic property is strong.But additive 5～25%, Solubilization of Water 5～30%.Can find out the microemulsion consumption more than 15% from specific embodiment, the water yield only is 15%.The micro-emulsified fuel performance transparency that China Patent Publication No. CN101323801A, CN101412922A make is stable, but emulsifier is large, and water solubilization is few.
(3) the microemulsion nitrogen content is high, is unfavorable for reducing the NOx discharging, also can have a negative impact to equipment.Relate to a kind of micro emulsion diesel fuel composite additive such as China Patent Publication No. CN1394941A, wherein contain strong aqua 15～20%, Monoethanolamine MEA BASF 1～5%, trap 6～10%.Although additive 12%, Solubilization of Water 30% has solved that to add agent many, the problem that water mixing is few, and nitrogen element content is higher in the additive, is unfavorable for reducing the NOx discharging, also can aggravate equipment corrosion and wearing and tearing.China Patent Publication No. CN1560200A relates to a kind of micro emulsion diesel fuel and production method thereof of producing with petrochemical industry alkali refining waste water, wherein refined by vitriol oil acidifying because reclaiming oil plant, so added 10～20% ammoniacal liquor, although waste water is fully used, but the nitrogen content in the diesel oil rises, and is unfavorable to environmental protection and equipment.
(4) the microemulsion raw material is difficult for obtaining, and the microemulsion flash-point is low.All relate to a kind of micro-emulsified biological diesel and preparation method thereof such as China Patent Publication No. CN101250431A, CN101348748A, good stability, but biofuel generally refined by the animal-plant oil of high-quality, price is expensive, methanol content is high, and is unfavorable to Flash Point of Diesel.Chinese patent application numbers 200910249921.0 relates to a kind of rare earth carboxylate micro-emulsified fuel additive, and rate of economizing gasoline reaches 5～13%, reduces exhaust emissions 40～95%, colloid and carbon deposit Vehicle Driving Cycle after 30 hours clearance rate be 92%.But rare earth carboxylate is not easy to obtain, and preparation is complicated.The microemulsion diesel water mixing agent of China Patent Publication No. CN101497832A invention, major surfaces promoting agent C12-18 fatty acid polyethylene (20) ether and OPE-15 consumption 4.9～5.6%, auxiliary agent methyl alcohol 4～5%.Can solubilized purified water purification 15～16%, this microemulsion can be preserved 1 year, and profit is not stratified.Microemulsion is the material such as containing metal, halogen not, also easily buying, but the auxiliary agent methanol usage is many, and very large on the Flash Point of Diesel impact, be unfavorable for storing and transportation.
(5) combustion processes easily produces colloid.All relate to a kind of micro-emulsified fuel that utilizes the sewer oil preparation such as China Patent Publication No. CN1766039A, CN101016471A, although cost is low, good stability is introduced sewer oil and extractive matter thereof, easily generates colloid during oil inflame.
(6) preparation is complicated, is unsuitable for industry and promotes.Micro-emulsion diesel as China Patent Publication No. CN1962826A, application number 200910230054.6 relate to need use ultrasonic wave during preparation, is unsuitable for industrialization promotion.China Patent Publication No. CN101469278A relates to microemulsion fuel of a kind of utilizing quantized carbon materials preparation and preparation method thereof, although can improve oil quality, improves combustion value, and preparation process is complicated.
[summary of the invention]
The object of the invention is to overcome the deficiencies in the prior art, the preparation method of a kind of diesel oil microemulsion and micro emulsion diesel fuel is provided.
The objective of the invention is to be achieved through the following technical solutions:
A kind of diesel oil microemulsion, its material component mass percent be,
Described ammoniacal liquor is that thanomin is replaced, and wherein, the mass percent of thanomin is 0.5%～1.0%;
Described lipid acid is acid number greater than 190.0 unsaturated fatty acids, i.e. animal oleic acid;
Described ammoniacal liquor is concentration greater than 25% analytical pure strong aqua;
Described thanomin is analytical pure;
Described Tween is nonionic surface active agent, is tween 80 or polysorbate85, is the commercially available prod;
Described Span is nonionic surface active agent, for span 20 or sorbester p17 or sapn 83, is the commercially available prod;
Described OP is nonionic surface active agent, for 0P series, is the commercially available prod;
A kind of micro emulsion diesel fuel, its material component mass percent be,
Described Organic Alcohol/or organic ether be one or more mixture in following: methyl alcohol, ethanol, n-propyl alcohol, propyl carbinol, isopropylcarbinol, Pentyl alcohol, primary isoamyl alcohol, n-hexyl alcohol, ethylene glycol, 1,2-PD and ethylene glycol-methyl ether;
Described diesel oil is preferably 0# diesel oil;
A kind of preparation method of micro emulsion diesel fuel is: its concrete steps are,
At room temperature, (1) diesel oil microemulsion is composite by the mass percent of each component; (2) ratio of complex microemulsion in mass percent 3.0%～6.0% added in the diesel oil, vibration evenly; (3) ratio in mass percent 4.0%～20.0% adds entry and then in the diesel oil, and vibration evenly; (4) add Organic Alcohol/or organic ether in the ratio of mass percent 0.1%～2.0% in the most backward diesel oil, vibration evenly or adopt ultra-sonic dispersion namely obtains micro emulsion diesel fuel.
Because microemulsion is the stabilising system of spontaneous generation, during preparation, also can be with step (3), (4) exchange, and namely add first Organic Alcohol/or organic ether in the diesel oil, add at last entry.
Microemulsion of the present invention has following characteristics: (1) not metal ion, halogen and element sulphur etc. to the disadvantageous material of equipment; (2) belong to oxygenatedchemicals, be conducive to the perfect combustion of micro emulsion diesel fuel, reduce the discharging of carbon deposit and tail gas; (3) be chemical field tensio-active agent commonly used, the raw material abundance be easy to buying and price comparatively cheap comparatively speaking.
The present invention adopts anion surfactant and nonionogenic tenside composite, makes tensio-active agent arrange closelyr at interfacial film, and the tensio-active agent that adsorbs on the interface increases, and has improved the stability of water solubilization and micro emulsion drop.Use the micro emulsion diesel fuel that diesel oil microemulsion of the present invention is made, have the following advantages:
(1) the microemulsion consumption is few, and watering quantity is many, and preparation is simple, and cost is low;
(2) character and pure diesel oil are more or less the same, and atomization is good, are neutral, to engine without corrosion;
(3) can be miscible within the specific limits with pure diesel oil, if therefore use micro emulsion diesel fuel, pure diesel oil remaining in fuel tank or the oil circuit need not thoroughly be removed;
(4) in 0～80 ℃, stable in properties, but standing storage.According to pertinent literature, diesel engine normal operation 1 hour, the temperature of fuel tank generally can not be higher than 20 ℃ of envrionment temperatures, and therefore the profit layering can not occur in measurable product of the present invention in diesel engine, thereby the discontinuity that causes Fuel Injection Mechanism of Diesel Engine, the non-normal working of initiation diesel engine;
[embodiment]
The preparation method's of a kind of diesel oil microemulsion of the present invention and micro emulsion diesel fuel embodiment below is provided.
Embodiment 1
The micro emulsion diesel fuel water content is 10.4% diesel oil microemulsion and the preparation of micro emulsion diesel fuel
(1) preparation of diesel oil microemulsion
In a 100ml Erlenmeyer flask, add successively oleic acid 0.50 gram, ammoniacal liquor 00.6 gram, tween 80 0.39 gram, sorbester p17 0.25 gram, OP-4 1.3 grams, vibration evenly dissolves emulsifying agent fully.
(2) preparation of micro emulsion diesel fuel
Under the room temperature, in a 100ml Erlenmeyer flask, take by weighing 0# diesel oil 42.5 grams, then get above-mentioned diesel oil microemulsion 2.5 grams and add Erlenmeyer flask, vibration evenly adds water 5.24 grams while vibrating, add subsequently 0.13 gram Pentyl alcohol, if the employing mode of oscillation then namely obtains translucent diesel oil microemulsion after 7 hours; If carry out ultra-sonic dispersion, ultrasonic parameters is: 40KHz, and 20min, 25 ℃, 127W then leaves standstill 10min and can obtain translucent micro emulsion diesel fuel.
Embodiment 2
The micro emulsion diesel fuel water content is 10.0% diesel oil microemulsion and the preparation of micro emulsion diesel fuel
(1) preparation of diesel oil microemulsion
In a 100ml Erlenmeyer flask, add successively oleic acid 0.55 gram, ammoniacal liquor 0.06 gram, polysorbate85 0.16 gram, span 20 0.23 gram, OP-4 1.27 grams, vibration evenly dissolves emulsifying agent fully.
(2) preparation of micro emulsion diesel fuel
Under the room temperature, in a 100ml Erlenmeyer flask, take by weighing 0# diesel oil 42.5 grams, then get above-mentioned diesel oil microemulsion and add Erlenmeyer flask, vibration evenly adds water 5.00 grams while vibrating, add subsequently 0.18 gram Pentyl alcohol, vibration evenly obtains translucent micro emulsion diesel fuel at last.
Embodiment 3
The micro emulsion diesel fuel water content is 10.2% diesel oil microemulsion and the preparation of micro-emulsion diesel
(1) preparation of diesel oil microemulsion
In a 100ml Erlenmeyer flask, add successively oleic acid 0.18 gram, thanomin 0.02 gram, polysorbate85 0.18 gram, sapn 83 0.22 grams, OP-4 1.64 grams, vibration evenly dissolves emulsifying agent fully.
(2) preparation of micro emulsion diesel fuel
Under the room temperature, in a 100ml Erlenmeyer flask, take by weighing 0# diesel oil 42.5 grams, then get above-mentioned diesel oil microemulsion and add Erlenmeyer flask, vibration evenly adds water 5.08 grams while vibrating, add subsequently 0.10 gram Pentyl alcohol, vibration evenly obtains translucent micro emulsion diesel fuel at last.
The microemulsion of the present invention's preparation not metal ion, halogen and element sulphur etc. belongs to oxygenatedchemicals to equipment and the disadvantageous material of environment, helps the perfect combustion of micro emulsion diesel fuel, improves efficiency of combustion.Microemulsion preparation is simple, and cost is low, but standing storage, can be miscible within the specific limits with pure diesel oil, and significantly reduce the discharging of the tail gas such as solid particulate, CO, NOx, help environment protection.
The above only is preferred implementation of the present invention; should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise; can also make some improvements and modifications, these improvements and modifications also should be considered within the scope of protection of the present invention.
Claims (10)
1. a diesel oil microemulsion is characterized in that, the material component mass percent is,
2. a kind of diesel oil microemulsion as claimed in claim 1 is characterized in that, described ammoniacal liquor is that thanomin is replaced, and the mass percent of thanomin is 0.5%～1.0%.
3. a kind of diesel oil microemulsion as claimed in claim 1 is characterized in that, described lipid acid is acid number greater than 190.0 unsaturated fatty acids, i.e. animal oleic acid.
4. a kind of diesel oil microemulsion as claimed in claim 1 is characterized in that, described Tween is nonionic surface active agent.
5. a kind of diesel oil microemulsion as claimed in claim 1 is characterized in that, described Span is nonionic surface active agent.
6. a kind of diesel oil microemulsion as claimed in claim 1 is characterized in that, described OP is nonionic surface active agent.
7. a micro emulsion diesel fuel is characterized in that, the material component mass percent is,
8. a kind of micro emulsion diesel fuel as claimed in claim 7, it is characterized in that, described Organic Alcohol/or organic ether be one or more mixture in following: methyl alcohol, ethanol, n-propyl alcohol, propyl carbinol, isopropylcarbinol, Pentyl alcohol, primary isoamyl alcohol, n-hexyl alcohol, ethylene glycol, 1,2-PD and ethylene glycol-methyl ether.
9. the preparation method of a micro emulsion diesel fuel is characterized in that, its concrete steps are,
At room temperature, (1) diesel oil microemulsion is composite by the mass percent of each component; (2) ratio of complex microemulsion in mass percent 3.0%～6.0% added in the diesel oil, vibrate evenly or the employing ultra-sonic dispersion; (3) ratio in mass percent 4.0%～20.0% adds entry and then in the diesel oil, and vibration evenly or adopt ultra-sonic dispersion; (4) add Organic Alcohol/or organic ether in the ratio of mass percent 0.1%～2.0% in the most backward diesel oil, vibration evenly or adopt ultra-sonic dispersion namely obtains micro emulsion diesel fuel.
10. the preparation method of a kind of micro emulsion diesel fuel as claimed in claim 9 is characterized in that, with step (3), (4) exchange, and namely adds first Organic Alcohol/or organic ether in the diesel oil, adds at last entry.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104263440A (en) * | 2014-09-17 | 2015-01-07 | 湖州科达化工燃料有限公司 | Diesel microemulsion and preparation method thereof |
| CN104726150A (en) * | 2015-02-13 | 2015-06-24 | 宁波柯林菲尔节能环保科技有限公司 | Fuel oil micro-emulsifier and preparation method thereof |
| CN105985821A (en) * | 2015-02-11 | 2016-10-05 | 上海欣页化工科技有限公司 | Microemulsion-type diesel oil additive, microemulsion-type diesel oil and preparation method of microemulsion-type diesel oil |
| CN107163999A (en) * | 2017-06-19 | 2017-09-15 | 刘政吉 | A kind of fuel catalytic hydrogen-oxygen liquid |
| CN109181795A (en) * | 2018-10-08 | 2019-01-11 | 乐柴能源有限公司 | A kind of mixed type fuel oil flash point enhancer |
| CN110184109A (en) * | 2019-05-21 | 2019-08-30 | 大连理工大学 | Low smoke intensity micro emulsion diesel fuel and preparation method thereof |
| CN110551539A (en) * | 2018-03-16 | 2019-12-10 | 朱觉锦 | Emulsified fuel oil for gas suspension effect internal combustion engine and internal combustion engine |
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| CN101177638A (en) * | 2007-12-01 | 2008-05-14 | 鞍山市佳良能源技术开发有限公司 | Clean diesel fuel additive |
| KR100829844B1 (en) * | 2007-04-18 | 2008-05-16 | 오상규 | Preparing system of emulsified fuel for decreasing greenhouse gases |
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| CN104263440A (en) * | 2014-09-17 | 2015-01-07 | 湖州科达化工燃料有限公司 | Diesel microemulsion and preparation method thereof |
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| CN107163999A (en) * | 2017-06-19 | 2017-09-15 | 刘政吉 | A kind of fuel catalytic hydrogen-oxygen liquid |
| CN110551539A (en) * | 2018-03-16 | 2019-12-10 | 朱觉锦 | Emulsified fuel oil for gas suspension effect internal combustion engine and internal combustion engine |
| CN109181795A (en) * | 2018-10-08 | 2019-01-11 | 乐柴能源有限公司 | A kind of mixed type fuel oil flash point enhancer |
| CN110184109A (en) * | 2019-05-21 | 2019-08-30 | 大连理工大学 | Low smoke intensity micro emulsion diesel fuel and preparation method thereof |
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