CN103555381B - Diesel oil reverse micelle system, preparation method, application and biofuel and preparation method - Google Patents
Diesel oil reverse micelle system, preparation method, application and biofuel and preparation method Download PDFInfo
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Abstract
The present invention relates to a kind of diesel oil reverse micelle system, preparation method, application and biofuel and preparation method, diesel oil reverse micelle system is by rhamnolipid, diesel oil, cosurfactant and water composition, take diesel oil as solvent, rhamnolipid concentration is 30 ~ 75g/L, cosurfactant concentration is 15 ~ 60g/L, the concentration of water is 24 ~ 30mg/L, preparation method is for be dissolved in diesel oil by rhamnolipid, then cosurfactant and excessive water is added, make mixing, leave standstill, be separated, obtain diesel oil reverse micelle system, biofuel is that 80 ~ 95% diesel oil reverse micelle systems and 5 ~ 20% Viscotrol C form by volume proportion, preparation method is for join in diesel oil reverse micelle system by Viscotrol C, insulation vibration, centrifugal, be separated, obtain biofuel, the present invention utilizes diesel oil reverse micelle system mixing production of biodiesel from castor oil, do not change the chemical structure of Viscotrol C, preparation process non-secondary pollution, technique is simple.
Description
Technical field
The present invention relates to a kind of reverse micelle system and biofuel, specifically relate to a kind of diesel oil reverse micelle system, preparation method, application and biofuel and preparation method.
Background technology
Current China's oil external dependence degree has exceeded 50%, has exceeded national energy security barrier line.Along with the raising gradually of living standards of the people, the demand of China to oil is increasing, moreover, vehicle exhaust causes environmental aspect to go from bad to worse, so, find a kind of reproducible clean energy and seem more and more urgent, wherein biofuel causes the concern of countries in the world with recyclability and low emission.
Traditional biofuel for stock oil, makes the clean renewable diesel fuel that can replace petrifaction diesel with oil crops, animal grease, waste cooking oil and the waterplant such as Wild oil plant and engineering microalgae grease etc. by ester-exchange technology.But the cost of traditional biological diesel oil has 75% to depend on raw material, not only require that raw material has sufficient source, and require cheap.Viscotrol C is described as the world ten large one of oil plant and four large unedible oil plants, is considered as by people reproducible " green energy resource " that have very much potentiality to be exploited.There is oxidative rancidity phenomenon hardly in atmosphere in Viscotrol C, is typical non-drying liquid oils, has good preservation stability, there is high flash point, the characteristics such as high pour point, but the general grease viscosity of the viscosity ratio of Viscotrol C is high a lot, can not directly be used as vehicle fuel and use.
Northcentral University's academic dissertation, point out in " preparation of ricinus oil biological diesel oil and performance study thereof ", the main production process of biofuel has direct mixing method, microemulsion method, high temperature pyrolytic cracking, chemically catalyzed interesterification method.
In microemulsion method, point out that Neuma etc. is raw material by tensio-active agent (main component is soya-bean oil soap matter, dodecyl sodium sulfonate and fatty acid ethanolamide amine), cosurfactant (main component is ethyl, propyl group, isoamyl alcohol), water, refining diesel oil and soybean oil, develop the microemulsion system of alternative diesel oil, wherein consist of diesel oil 3.160g, character and the diesel oil of the Microemulsion System of soybean oil 0.790g, water 0.050g, primary isoamyl alcohol 0.338g, dodecyl sodium carbonate 0.676g are the most close.Point out, there is carbon distribution and made the problems such as lubricating oil viscosity increase in the biofuel of the preparation such as Ziejewski simultaneously in durability test.
The document of chemically catalyzed interesterification method production of biodiesel from castor oil have Chinese Patent Application No. be 200810150332.2 patent documentation, disclose one production of biodiesel from castor oil method, step is, be 1:6 by Viscotrol C and alcohol mol ratio, catalyst levels is that oil is heavy by 0.8 ~ 1%, react 1.5 ~ 6h at 45 ~ 65 DEG C, obtain biofuel.This ester exchange method is prepared biofuel and is belonged to chemical preparation process, has following shortcoming: complex process, alcohol must be excessive, and must have corresponding alcohol retrieving arrangement in subsequent technique, energy consumption is high, and equipment investment is large; Esterification products is difficult to reclaim, and cost recovery is high; Production process has waste lye to discharge, and can cause the shortcomings such as secondary pollution to environment.
Summary of the invention
In order to better utilised Viscotrol C does fuel, the invention provides a kind of diesel oil reverse micelle system, preparation method and the application in solubilising Viscotrol C biodiesel synthesis thereof, the present invention also provides a kind of biofuel and the preparation method that utilize the preparation after diesel oil reverse micelle system solubilising Viscotrol C.The present invention utilizes diesel oil reverse micelle system mixing production of biodiesel from castor oil, and do not change the chemical structure of Viscotrol C, preparation process non-secondary pollution, technique are simple, with low cost.Relative to biofuel prepared by other microemulsion methods, the present invention adopts rhamnolipid as tensio-active agent, environmental friendly regenerated property can be improved, biofuel can produce effect of micro-explosion, but not affecting other character (as corrodibility, high viscosity etc.) of biofuel, the biofuel of the present invention's synthesis has good stability.
The present invention is by the following technical solutions:
Diesel oil reverse micelle system, is made up of rhamnolipid, diesel oil, cosurfactant and water, take diesel oil as solvent, and rhamnolipid concentration is 30 ~ 75 g/L, and cosurfactant concentration is 15 ~ 60g/L, and water concentration is 24 ~ 30mg/L.Wherein, rhamnolipid concentration is 30 ~ 75g/L, represents in 1L solution have 30 ~ 75g rhamnolipid.
Described cosurfactant is preferably n-Heptyl alcohol or n-Octanol.
The present invention also provides a kind of preparation method of diesel oil reverse micelle system, and step is, is dissolved in diesel oil, then adds cosurfactant and excessive water, make mixing by stirring or ultrasonication by rhamnolipid, leaves standstill, and is separated, obtains diesel oil reverse micelle system.The described excessive water that adds refers to the amount adding and be greater than this due water in diesel oil reverse micelle system.
The present invention also provides the application of a kind of diesel oil reverse micelle system in solubilising Viscotrol C biodiesel synthesis.
The present invention also provides a kind of biofuel, is that 80 ~ 95% diesel oil reverse micelle systems and 5 ~ 20% Viscotrol C form by volume proportion.
The present invention also provides a kind of preparation method of biofuel, and step is, is joined by Viscotrol C in diesel oil reverse micelle system, insulation vibration, centrifugal, lower floor is residual phase, upper strata is diesel oil, Viscotrol C mixing microemulsion system after solubilising Viscotrol C, is separated, obtains biofuel.The temperature of described insulation is 35 ~ 60 DEG C, and the speed of described vibration is 120 ~ 210rpm, and duration of oscillation is 25 ~ 60min.Described centrifugal speed is 5000 ~ 7000rpm, and centrifugation time is 5 ~ 7min.
Described diesel oil is preferably GB 0# diesel oil, and rhamnolipid is purity >=90% grade, and cosurfactant is analytical pure, and Viscotrol C is commercially available technical grade product.
Beneficial effect of the present invention is:
1. the Viscotrol C of the present invention not only wide material sources, and self there is good preservation stability, there is oxidative rancidity phenomenon hardly in atmosphere, thus ensure that the biofuel of generation has satisfactory stability, at room temperature can long-time storage, keep stable, not stratified at-20 ~ 40 DEG C.The rhanolipid as biosurfactant used has good chemistry and biological nature concurrently, there is oil, water is amphipathic, oil water interfacial tension can be reduced, difference maximum compared with chemical surfactant is, it is by the nontoxic material of microorganisms producing, this not only greatly reduces the cost of production biofuel, also improves environmental-protecting performance.
2. the environment-friendly type biodiesel formed by diesel oil reverse micelle system solubilising Viscotrol C can reduce the full-bodied shortcoming of Viscotrol C, it is made normally to be used in diesel engine, because the reverse micelle system formed is a kind of water in oil microemulsion, effect of micro-explosion can be produced, improve the efficiency of combustion of biofuel, reduce pollutent and produce concentration.The principle of described effect of micro-explosion is, diesel oil reverse micelle system is a kind of water in oil microemulsion, when oil droplet is heated, because the boiling point difference of water and oil is larger, therefore, water is first vaporized, and volume sharply expands, moment splits into the less oil droplet of many particle diameters wrapping in outside oil phase, and this process is exactly " microexplosion ".The effect of microexplosion is exactly make oil droplet granular more, improves the apparent activation energy of oil droplet, thus accelerates the volatilization of oil droplet, enables oil droplet Thorough combustion, improves the discharge of efficiency of combustion and reduction pollutent.The environment-friendly type biodiesel of synthesis has that stability is high, flash-point is high, viscosity is low, corrodibility is low, efficiency of combustion advantages of higher.In addition, because rhamnolipid and Viscotrol C are renewable, nontoxic environment-friendly type material, the high-environmental of biofuel can therefore be ensured.
3. the technique that adopts of the present invention is relative to the production technique of traditional biological diesel oil, and more simply, fast, production process non-secondary pollution, not only reduces production cost, also improves the feature of environmental protection.
4. the present invention maximum can the Viscotrol C of solubilising 20% in diesel oil reverse micelle system, biofuel can at room temperature long-time storage, keeps stable, not stratified at-20 ~ 40 DEG C; Viscosity, the corrodibility of biofuel are suitable with diesel oil with condensation point, and flash-point improves a lot compared to diesel oil, and calorific value, a little less than diesel oil, overcomes the shortcoming that Viscotrol C can not directly apply to existing diesel; The reverse micelle system synthesized in the present invention is a kind of water in oil microemulsion, and its water ratio, about 1.3%, can produce effect of micro-explosion during burning, improves the efficiency of combustion of biofuel, reduces pollutent and produces concentration.
embodiment:
Below in conjunction with specific embodiment, the invention will be further described, but protection domain not thereby limiting the invention.
Embodiment 1
Diesel oil reverse micelle system, is made up of 2.5g rhamnolipid, 45.0ml diesel oil, 1.5g n-Octanol and 1.2mL water.
The preparation method of diesel oil reverse micelle system is, taking 2.5g rhamnolipid joins in 45.0mL diesel oil, ultrasonicly dissolve completely to rhamnolipid, solution clarification is bright, then in rhamnolipid-diesel oil solution, slowly adds 1.5g n-Octanol, add 1.2mL ultrapure water again, after shaking up, leave standstill for some time, solution is clarified gradually, excessive water been separated in lower floor, is separated and obtains diesel oil reverse micelle system.
Embodiment 2
Biofuel, by 42.5ml diesel oil reverse micelle system, 7.5ml Viscotrol C forms.
The preparation method of biofuel is, diesel oil reverse micelle system 42.5mL prepared by Example 1, slowly adds wherein by 7.5mL Viscotrol C, after shaking up, be positioned in constant water bath box the 30min that vibrates, temperature controls at 40 DEG C, and oscillation rate controls at 180rpm, solution appeared cloudy state after vibration, then centrifugal 6min under 6000rpm, makes it accelerate layering, and after centrifugal, solution is divided into two-layer, lower floor is impurity layer, and upper strata is biofuel.
The biofuel that the present embodiment obtains, at 30 DEG C, record kinetic viscosity with the SNB-2 type digital viscometer instrument under smart sky brand is 7.89 mpas, its value is a little more than diesel oil viscosity number (diesel oil range of viscosities is 3 ~ 8mpas), record corrodibility by GB/T 5096 copper strip test identical with diesel oil, be 1a; Flash-point utilizes GB/T 3536 method to be measured as 125 DEG C, and recording water ratio by Ka Shi reagent method is about 1.3%; Can at room temperature seal stably stored more than 3 months, biofuel still keeps clarification bright, and the kinetic viscosity after 3 months is only increased to 8.96 mpas, keeps stable, not stratified at-20 ~ 40 DEG C.
Embodiment 3
Diesel oil reverse micelle system, is made up of 1.5g rhamnolipid, 45.0ml diesel oil, 0.9g n-Octanol and 1.2mL water.
Preparation method is, taking 1.5g rhamnolipid joins in 45.0mL diesel oil, ultrasonicly dissolve completely to rhamnolipid, solution clarification is bright, then in rhamnolipid-diesel oil solution, slowly adds 0.9g n-Octanol, add 1.2mL ultrapure water again, stir, leave standstill for some time, solution will be clarified gradually, excessive water been separated in lower floor, is separated and obtains diesel oil reverse micelle system.
Embodiment 4
Biofuel, is made up of 45.0ml diesel oil reverse micelle system and 5.0ml Viscotrol C.
The preparation method of biofuel is, diesel oil reverse micelle system 45.0mL prepared by Example 3, slowly adds wherein by 5.0mL Viscotrol C, after shaking up, be positioned in constant water bath box the 25min that vibrates, temperature controls at 40 DEG C, and oscillation rate controls at 150rpm, solution appeared cloudy state after vibration, then centrifugal 5min under 5500rpm, makes it accelerate layering, and after centrifugal, solution is divided into two-layer, lower floor is impurity layer, and upper strata is biofuel.
The biofuel that the present embodiment obtains, at 30 DEG C, record kinetic viscosity with the SNB-2 type digital viscometer instrument under smart sky brand is 6.27 mpas, its value, a little more than diesel oil viscosity number, records corrodibility by GB/T 5096 copper strip test identical with diesel oil, is 1a; Flash-point utilizes GB/T 3536 to be measured as 107 DEG C, and recording water ratio by Ka Shi reagent method is about 1.2%; Can at room temperature seal stably stored more than 3 months, biofuel still keeps clarification bright, and the kinetic viscosity after 3 months is only increased to 6.93 mpas, keeps stable, not stratified at-20 ~ 40 DEG C.
Embodiment 5
Diesel oil reverse micelle system, is made up of 3.5g rhamnolipid, 45.0ml diesel oil, 2.1g n-Octanol and 1.2mL water.
Preparation method is, taking 3.5g rhamnolipid joins in 45.0mL diesel oil, ultrasonicly dissolve completely to rhamnolipid, solution clarification is bright, then in rhamnolipid-diesel oil solution, slowly adds 2.1g n-Octanol, add 1.2mL ultrapure water again, after shaking up, leave standstill for some time, solution will be clarified gradually, excessive water been separated in lower floor, is separated and obtains diesel oil reverse micelle system.
Embodiment 6
Biofuel, is made up of 40.0ml diesel oil reverse micelle system and 10ml Viscotrol C.
The preparation method of biofuel is, diesel oil reverse micelle system 40.0mL prepared by Example 5, slowly adds wherein by 10mL Viscotrol C, after shaking up, be positioned in constant water bath box the 45min that vibrates, temperature controls at 40 DEG C, and oscillation rate controls at 210rpm, solution appeared cloudy state after vibration, then centrifugal 7min under 7000rpm, makes it accelerate layering, and after centrifugal, solution is divided into two-layer, lower floor is impurity layer, and upper strata is biofuel.
The biofuel that the present embodiment obtains, at 30 DEG C, record kinetic viscosity with the SNB-2 type digital viscometer instrument under smart sky brand is 10.2 mpas, its value, a little more than diesel oil viscosity number, records corrodibility by GB/T 5096 copper strip test identical with diesel oil, is 1a; Flash-point utilizes GB/T 3536 to be measured as 143 DEG C, and recording water ratio by Ka Shi reagent method is about 1.3%; Can at room temperature seal stably stored more than 3 months, biofuel still keeps clarification bright, and the kinetic viscosity after 3 months is only increased to 11.6 mpas, keeps stable, not stratified at-20 ~ 40 DEG C.
Embodiment 7
Diesel oil reverse micelle system, is made up of 2.5g rhamnolipid, 45.0ml diesel oil, 2.0g n-Heptyl alcohol and 1.2mL water.
Preparation method is, taking 2.5g rhamnolipid joins in 45.0mL diesel oil, ultrasonicly dissolve completely to rhamnolipid, solution clarification is bright, then in rhamnolipid diesel oil solution, slowly adds 2.0g n-Heptyl alcohol, add 1.2mL ultrapure water again, after shaking up, leave standstill for some time, solution will be clarified gradually, excessive water been separated in lower floor, is separated and obtains diesel oil reverse micelle system.
Embodiment 8
Biofuel, is made up of 42.5ml diesel oil reverse micelle system and 7.5ml Viscotrol C.
The preparation method of biofuel is, diesel oil reverse micelle system 42.5mL prepared by Example 7, slowly adds wherein by 7.5mL Viscotrol C, after shaking up, be positioned in constant water bath box the 30min that vibrates, temperature controls at 35 DEG C, and oscillation rate controls at 180rpm, solution appeared cloudy state after vibration, then centrifugal 6min under 5500rpm, makes it accelerate layering, and after centrifugal, solution is divided into two-layer, lower floor is impurity layer, and upper strata is biofuel.
The biofuel that the present embodiment obtains, at 30 DEG C, record kinetic viscosity with the SNB-2 type digital viscometer instrument under smart sky brand is 7.68 mpas, its value, a little more than diesel oil viscosity number, records corrodibility by GB/T 5096 copper strip test identical with diesel oil, is 1a; Flash-point utilizes GB/T 3536 to be measured as 123 DEG C, and recording water ratio by Ka Shi reagent method is about 1.3%; Can at room temperature seal stably stored more than 3 months, biofuel still keeps clarification bright, and the kinetic viscosity after 3 months is only increased to 8.96 mpas, keeps stable, not stratified at-20 ~ 40 DEG C.
Embodiment 9
Diesel oil reverse micelle system, is made up of 1.5g rhamnolipid, 45.0ml diesel oil, 1.2g n-Heptyl alcohol and 1.2mL water.
A method for diesel oil reversed micelle system solubilising Viscotrol C synthetic environment-friendly biofuel, comprises the following steps:
Preparation method is, taking 1.5g rhamnolipid joins in 45.0mL diesel oil, ultrasonicly dissolve completely to rhamnolipid, solution clarification is bright, then in rhamnolipid diesel oil solution, slowly adds 1.2g n-Heptyl alcohol, add 1.2mL ultrapure water again, after shaking up, leave standstill for some time, solution will be clarified gradually, excessive water been separated in lower floor, is separated and obtains diesel oil reverse micelle system.
Embodiment 10
Biofuel, is made up of 45.0ml diesel oil reverse micelle system and 5ml Viscotrol C.
The preparation method of biofuel is, diesel oil reverse micelle system 45.0mL prepared by Example 9, slowly adds wherein by 5mL Viscotrol C, after shaking up, be positioned in constant water bath box the 25min that vibrates, temperature controls at 35 DEG C, and oscillation rate controls at 150rpm, solution appeared cloudy state after vibration, then centrifugal 5min under 5000rpm, makes it accelerate layering, and after centrifugal, solution is divided into two-layer, lower floor is impurity layer, and upper strata is biofuel.
The biofuel that the present embodiment obtains, at 30 DEG C, record kinetic viscosity with the SNB-2 type digital viscometer instrument under smart sky brand is 6.15 mpas, its value, a little more than diesel oil viscosity number, records corrodibility by GB/T 5096 copper strip test identical with diesel oil, is 1a; Flash-point utilizes GB/T 3536 to be measured as 104 DEG C, and recording water ratio by Ka Shi reagent method is about 1.3%; Can at room temperature seal stably stored more than 3 months, biofuel still keeps clarification bright, and the kinetic viscosity after 3 months is only increased to 6.84 mpas, keeps stable, not stratified at-20 ~ 40 DEG C.
Embodiment 11
Diesel oil reverse micelle system, is made up of 3.5g rhamnolipid, 45.0ml diesel oil, 2.8g n-Heptyl alcohol and 1.2mL water.
Preparation method is, taking 3.5g rhamnolipid joins in 45.0mL diesel oil, ultrasonicly dissolve completely to rhamnolipid, solution clarification is bright, then in rhamnolipid diesel oil solution, slowly adds 2.8g n-Heptyl alcohol, add 1.2mL ultrapure water again, after shaking up, leave standstill for some time, solution will be clarified gradually, excessive water been separated in lower floor, is separated and obtains diesel oil reverse micelle system.
Embodiment 12
Biofuel, is made up of 40.0ml diesel oil reverse micelle system and 10ml Viscotrol C.
The preparation method of biofuel is, Example 11 prepare diesel oil reversed micelle system 40.0mL, slowly 10mL Viscotrol C is added wherein, after shaking up, be positioned in constant water bath box the 45min that vibrates, temperature controls at 35 DEG C, and oscillation rate controls at 210rpm, solution appeared cloudy state after vibration, then centrifugal 7min under 6500rpm, makes it accelerate layering, and after centrifugal, solution is divided into two-layer, lower floor is impurity layer, and upper strata is biofuel.
The biofuel that the present embodiment obtains, at 30 DEG C, record kinetic viscosity with the SNB-2 type digital viscometer instrument under smart sky brand is 10.5 mpas, its value, a little more than diesel oil viscosity number, records corrodibility by GB/T 5096 copper strip test identical with diesel oil, is 1a; Flash-point utilizes GB/T 3536 to be measured as 141 DEG C, and recording water ratio by Ka Shi reagent method is about 1.3%; Can at room temperature seal stably stored more than 3 months, biofuel still keeps clarification bright, and the kinetic viscosity after 3 months is only increased to 11.9 mpas, keeps stable, not stratified at-20 ~ 40 DEG C.
Below be only the preferred embodiment of the present invention, protection scope of the present invention be not only confined to above-described embodiment, all technical schemes belonged under thinking of the present invention all belong to protection scope of the present invention.It should be pointed out that for those skilled in the art, some improvements and modifications without departing from the principles of the present invention, should be considered as protection scope of the present invention.
Claims (6)
1., by a biofuel prepared by diesel oil reverse micelle system, it is characterized in that, described biofuel by volume proportion be 80 ~ 95% diesel oil reverse micelle systems and 5 ~ 20% Viscotrol C form; Described diesel oil reverse micelle system is made up of rhamnolipid, diesel oil, cosurfactant and water, take diesel oil as solvent, and rhamnolipid concentration is 30 ~ 75 g/L, and cosurfactant concentration is 15 ~ 60 g/L, and the concentration of water is 24 ~ 30mg/L.
2. biofuel as claimed in claim 1, it is characterized in that, described cosurfactant is n-Heptyl alcohol or n-Octanol.
3. a preparation method for biofuel as claimed in claim 1 or 2, is characterized in that, step is, is dissolved in by rhamnolipid in diesel oil, then adds cosurfactant and excessive water, makes mixing, leaves standstill, and is separated, obtains diesel oil reverse micelle system; Viscotrol C is joined in diesel oil reverse micelle system, insulation vibration, centrifugal, be separated, obtain biofuel.
4. the preparation method of biofuel as claimed in claim 3, it is characterized in that, the temperature of described insulation is 35 ~ 60 DEG C.
5. the preparation method of biofuel as claimed in claim 3, it is characterized in that, the speed of described vibration is 120 ~ 210rpm.
6. the preparation method of biofuel as claimed in claim 3, it is characterized in that, described centrifugal speed is 5000 ~ 7000rpm.
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