CN104531244B - A kind of micro-emulsified biological diesel - Google Patents

A kind of micro-emulsified biological diesel Download PDF

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CN104531244B
CN104531244B CN201510022784.2A CN201510022784A CN104531244B CN 104531244 B CN104531244 B CN 104531244B CN 201510022784 A CN201510022784 A CN 201510022784A CN 104531244 B CN104531244 B CN 104531244B
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micro
composite emulsifier
water
biological diesel
biofuel
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CN104531244A (en
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陈燕国
陈新宜
蔡胜
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HUANG JIAHENG
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Abstract

The present invention discloses a kind of micro-emulsified biological diesel and preparation method thereof, and micro-emulsified biological diesel of the present invention has high-moisture low viscosity, strong volatility, stable advantage.

Description

A kind of micro-emulsified biological diesel
Technical field
the present invention relates to a kind of biofuel, concrete a kind of micro-emulsified biological diesel.
Background technology
Biofuel is a kind of renewable and New-type fuel that security is high, and it is the liquid fuel made for raw material with the oil plant waterplant such as oil-yielding shrubs fruit, engineering microalgae such as the oil crops such as soybean and Semen Brassicae campestris, oil palm and Chinese pistache and animal grease, biodiesel etc.Biofuel can, to mix than with petrifaction diesel arbitrarily, be the petroleum diesel surrogate of high-quality.
But biofuel also has its shortcoming, as higher in biofuel viscosity, volatility is poor, NOx discharge is also higher and calorific value is low.And micro-emulsified biological diesel effectively can reduce the viscosity of biofuel, improve atomization, reduce NOx and soot emissions.
Micro-emulsified biological diesel is by the spontaneous thermodynamically metastable fixed system formed of biofuel, emulsifying agent (tensio-active agent) and water.Finding suitable emulsifying agent (tensio-active agent) is the key preparing stable micro-emulsified biological diesel, and in addition, appropriate oil, water and emulsifying agent (tensio-active agent) ratio are also one of key factors affecting micro-emulsified biological diesel performance.
Current micro-emulsified biological diesel technical study achieves some achievements, but still there is certain defect.Such as: grandson's equality (CN10140773, a kind of environment-friendly type microemulsified biodiesel and compound method thereof) reports a kind of biofuel-water microemulsion composite by polyoxyethylene octylphenol ether OP-4 and OP-7; Wu Lin etc. (CN101250431, a kind of micro-emulsified biological diesel and preparation method thereof) have studied a kind of composite emulsifier by being dissolved into oleic acid after SPAN80 and TWEEN80 mixing, and water, biofuel, thanomin and solubility promoter mixed preparing form; High Yongjian etc. (CN10134874, a kind of micro-emulsified biological diesel and compound method thereof) have found a kind of preparation method of micro-emulsified biological diesel, the biofuel of the method preparation
Be made up of mineral diesel, animal grease, methyl alcohol, naphthenic acid, OP emulsifying agent, sodium laurylsulfonate, trolamine etc.
Although these formulas can both obtain micro-emulsified biological diesel, the problem such as all have that emulsifier is too much, volatile performance is poor or formula is too complicated.The micro emulsion diesel fuel that Chinese patent CN102382713A provides obviously can reduce emulsifier, but its micro emulsion diesel fuel still has the problems such as entropy height is unstable, viscosity is high, volatility is low.At present, international oil price lattice soar all the way, and petroleum resources are more nervous, therefore, study micro-emulsified biological diesel of good performance and not only can reduce costs, and can save energy and environmental protection, are extremely important and extremely urgent problems.
Summary of the invention
In view of this, the present invention discloses a kind of high-moisture low viscosity, strong volatility, stable micro emulsion diesel fuel.
Object of the present invention is achieved through the following technical solutions: a kind of micro-emulsified biological diesel, and its formula is made up of following each component: biofuel 61 ~ 85 parts, composite emulsifier 3 ~ 8 parts, 20 ~ 46 parts, water by weight; Described composite emulsifier comprise by weight 23% fatty alcohol-polyoxyethylene ether AEO-3,16% trans-resveratrol, the dimethyl maleate of 11%, the MALEIC ANHYDRIDE of 20% and 30% N.F,USP MANNITOL.
Fatty alcohol-polyoxyethylene ether AEO-3 is prior art, can form water in oil emulsified particle in biofuel.But for the biofuel of high-moisture, its water in oil emulsified particle must have larger particle diameter, poor stability and easily crumple, final oily water separation.Especially biofuel is when burning, and high temperature causes oil-emulsifying water system entropy of micro emulsion diesel fuel to raise and randomness rising, final microemulsified systems collapse.When being applied in oil engine, oily water separation, by the structure of damage oil engine, even causes the extinguishing that oil engine happens suddenly.Composite emulsifier of the present invention, trans-resveratrol can reduce specifically
The apparent activation energy of water, does not affect the surfactivity of biofuel to promote the gathering of water droplet, the surface making biofuel be wrapped in water droplet forms microemulsified particle.Butene dioic acid dimethyl ester and MALEIC ANHYDRIDE coordinate, the stability of microemulsified particle can be strengthened, especially MALEIC ANHYDRIDE at high temperature can be decomposed into the combustion-supporting materials such as carbon monoxide by water in catalysis microemulsified particle, avoid moisture too high and reduce the temperature reduction of micro-emulsified biological diesel in oil engine and burning-point cannot be reached, causing burning insufficient.The entropy that N.F,USP MANNITOL then can limit micro-emulsified biological diesel system under the burning situation of High Temperature High Pressure increases, and the stability of maintenance system, prevents oily water separation.The biofuel of raw material of the present invention can select any one prior art to obtain.
Described composite emulsifier its preparation method is for be heated to 100 DEG C by described N.F,USP MANNITOL, add described fatty alcohol-polyoxyethylene ether AEO-3 and trans-resveratrol, MALEIC ANHYDRIDE, the heating under pressure to 150 DEG C of 0.4 ~ 0.7MPa in the container of sealing, and keep 20 ~ 40min; Release container pressure also makes temperature be down to 50 DEG C, adds butene dioic acid dimethyl ester, keeps 60min to obtain described composite emulsifier.
Described sealed vessel can select any one high pressure resistant equipment to realize.High temperature and high pressure contributes to activating AE0-3, trans-resveratrol, MALEIC ANHYDRIDE, and three must be adopted high temperature and high pressure process simultaneously.
The present invention also provides a kind of method preparing described micro-emulsified biological diesel especially, comprise following operation: under mark condition, described composite emulsifier, water is added successively in biofuel, per minute passes into the air of 10L/ kg water to it, apply the UV-light of wavelength 200 ~ 275nm simultaneously to it, after process 140 ~ 200min, obtain described micro-emulsified biological diesel.
UV-irradiation can improve the activity of composite emulsifier, reduces the activation energy of biofuel and water generation emulsification, and the micro-emulsified biological diesel making it to be formed more evenly and not layering occurs.
Embodiment
The present invention to be described in further detail below in conjunction with embodiment for the ease of it will be appreciated by those skilled in the art that:
Embodiment 1
The present embodiment provides a kind of micro-emulsified biological diesel, and its formula is made up of following each component: biofuel 76 parts, composite emulsifier 5 parts, 47 parts, water by weight; Described composite emulsifier comprise by weight by
Weighing scale 23% fatty alcohol-polyoxyethylene ether AEO-3,16% trans-resveratrol, the dimethyl maleate of 11%, the MALEIC ANHYDRIDE of 20% and 30% N.F,USP MANNITOL.
Described composite emulsifier its preparation method, for described N.F,USP MANNITOL is heated to 100 DEG C, adds described fatty alcohol-polyoxyethylene ether AEO-3 and trans-resveratrol, MALEIC ANHYDRIDE, the heating under pressure to 150 DEG C of 0.5MPa in the container of sealing, and keeps 35min; Release container pressure also makes temperature be down to 50 DEG C, adds butene dioic acid dimethyl ester, keeps 60min to obtain described composite emulsifier.
A kind of method preparing above-mentioned micro-emulsified biological diesel, comprise following operation: under mark condition (temperature is 0 DEG C and pressure is 101.325 kPas), described composite emulsifier, water is added successively in biofuel, per minute passes into the air of 10L/ kg water to it, to its UV-light applying wavelength 200 ~ 275nm continuous wavelength, (the commercially available ultraviolet LED of 30W produces simultaneously, distance 5cm), obtain described micro-emulsified biological diesel after process 200min.
Embodiment 2
The present embodiment provides a kind of micro-emulsified biological diesel, and its formula is made up of following each component:
Biofuel 83 parts, composite emulsifier 3 parts, 48 parts, water by weight; Described composite emulsifier comprise by weight 23% fatty alcohol-polyoxyethylene ether AEO-3,16% trans-resveratrol, the dimethyl maleate of 11%, the MALEIC ANHYDRIDE of 20% and 30% N.F,USP MANNITOL.
Described composite emulsifier its preparation method, for described N.F,USP MANNITOL is heated to 100 DEG C, adds described fatty alcohol-polyoxyethylene ether AEO-3 and trans-resveratrol, MALEIC ANHYDRIDE, the heating under pressure to 150 DEG C of 0.7MPa in the container of sealing, and keeps 30min; Release container pressure also makes temperature be down to 50 DEG C, adds butene dioic acid dimethyl ester, keeps 60min to obtain described composite emulsifier.
The micro emulsion diesel fuel of the present embodiment evenly obtains for being added in machine mixer by various raw material to be stirred to.
Embodiment 3
The present embodiment provides a kind of micro-emulsified biological diesel, and its formula is made up of following each component:
Biofuel 61 parts, composite emulsifier 4 parts, 36 parts, water by weight; Described composite emulsifier comprise by weight 23% fatty alcohol-polyoxyethylene ether AEO-3,16% trans-resveratrol, the dimethyl maleate of 11%, the MALEIC ANHYDRIDE of 20% and 30% N.F,USP MANNITOL.
Described composite emulsifier its preparation method, for described N.F,USP MANNITOL is heated to 100 DEG C, adds described fatty alcohol-polyoxyethylene ether AEO-3 and trans-resveratrol, MALEIC ANHYDRIDE, the heating under pressure to 150 DEG C of 0.6MPa in the container of sealing, and keeps 40min; Release container pressure also makes temperature be down to 50 DEG C, adds butene dioic acid dimethyl ester, keeps 60min to obtain described composite emulsifier.
The preparation method of the present embodiment is consistent with embodiment 1.
Comparative example 1
This comparative example provides a kind of micro-emulsified biological diesel.Change micro-emulsified biological diesel by application number by 200810047153.6 Chinese patents are provided.Water content 25wt%.
Comparative example 2
This comparative example provides a kind of micro-emulsified biological diesel, and its formula is made up of following each component:
Biofuel 76 parts, composite emulsifier 5 parts, 47 parts, water by weight; Described composite emulsifier comprise by weight 23% fatty alcohol-polyoxyethylene ether AEO-3, the dimethyl maleate of 19%, the MALEIC ANHYDRIDE of 28% and 30% N.F,USP MANNITOL.
Comparative example 3
This comparative example provides a kind of micro-emulsified biological diesel, and its formula is made up of following each component:
Biofuel 76 parts, composite emulsifier 5 parts, 47 parts, water by weight; Described composite emulsifier comprise by weight 28% fatty alcohol-polyoxyethylene ether AEO-3, the trans-resveratrol of 21%, the dimethyl maleate of 16% and 35% N.F,USP MANNITOL.
Comparative example 4
This comparative example provides a kind of micro-emulsified biological diesel, and its formula is made up of following each component:
Biofuel 76 parts, composite emulsifier 5 parts, 47 parts, water by weight; Described composite emulsifier comprise by weight 33% fatty alcohol-polyoxyethylene ether AEO-3,26% trans-resveratrol, the butene dioic acid dimethyl ester of 21%, the MALEIC ANHYDRIDE of 20%.
Emulsifying effectiveness and system stability test.
By the biofuel that comparative example and comparative example provide, fill in the measuring cup of 4 1000mL respectively, carry out following process respectively for individual group: the volume v1 observing the water separated bottom it, record its volume reduction simultaneously.Measuring cup is placed in the shading environment of 30 DEG C, records the volume v2 of the water that sub-argument goes out bottom measuring cup after 50 days.Micro emulsion diesel fuel in measuring cup is heated to 50 DEG C, records the volume v3 of isolated water bottom measuring cup after 5 days.Micro emulsion diesel fuel in measuring cup is heated to 80 DEG C, record 5 as a child measuring cup bottom part from the volume v4 of water outlet.Its result is as shown in table 1.
Table 1.
Acid number is tested.
Potassium hydroxide is adopted to be the acid number that biofuel is respectively organized in standard testing respectively.Its result is as shown in table 2.
Table 2.
Volatility is tested.
The micro emulsion diesel fuel of embodiment 1-3 is drawn 5ml, and dripping at radius is in the furnace pot of 3cm, 60 DEG C, relative humidity is that the pressure of 50%, standard atmosphere leaves standstill.Micro emulsion diesel fuel required time of volatilizing completely is respectively 380 seconds, 421 seconds, 411 seconds.
Kinematic viscosity, flash-point are tested.
Adopt kinematic viscosity, flash-point during 40 DEG C of GB/T265-1988 and GB/T261-2008 testing example 1-3.Its result is as table 3.
Table 3.
Be more than wherein specific implementation of the present invention, it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these apparent replacement forms all belong to protection scope of the present invention.

Claims (1)

1. a micro-emulsified biological diesel, its formula is made up of following each component:
Biofuel 61 ~ 85 parts, composite emulsifier 3 ~ 8 parts, 30 ~ 50 parts, water by weight; Described composite emulsifier comprise by weight 23% fatty alcohol-polyoxyethylene ether AEO-3,16% trans-resveratrol, the dimethyl maleate of 11%, the MALEIC ANHYDRIDE of 20% and 30% N.F,USP MANNITOL; Described composite emulsifier its preparation method is for be heated to 100 DEG C by described N.F,USP MANNITOL, add described fatty alcohol-polyoxyethylene ether AEO-3 and trans-resveratrol, MALEIC ANHYDRIDE, the heating under pressure to 150 DEG C of 0.4 ~ 0.7MPa in the container of sealing, and keep 20 ~ 40min; Release container pressure also makes temperature be down to 50 DEG C, adds dimethyl maleate, keeps 60min to obtain described composite emulsifier; The preparation method of described micro-emulsified biological diesel comprises following operation: under mark condition, described composite emulsifier, water is added successively in biofuel, per minute passes into the air of 10L/ kg water to it, apply the UV-light of wavelength 200 ~ 275nm simultaneously to it, after process 140 ~ 200min, obtain described micro-emulsified biological diesel.
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Publication number Priority date Publication date Assignee Title
CN106281481A (en) * 2016-08-23 2017-01-04 陈晓锋 A kind of biodiesel composite emulsifier and its preparation method and application
CN106190376A (en) * 2016-08-23 2016-12-07 陈晓锋 A kind of diesel oil emulsifier and its preparation method and application

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101250431A (en) * 2008-03-27 2008-08-27 武汉科技大学 Micro-emulsified biological diesel and preparation method thereof
CN102295966A (en) * 2011-07-25 2011-12-28 青岛福瑞斯生物能源科技开发有限公司 Micro-emulsified biodiesel and preparation method thereof
CN102382697A (en) * 2011-10-09 2012-03-21 国家石油石化产品质量监督检验中心(广东) Micro-emulsion biodiesel and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101250431A (en) * 2008-03-27 2008-08-27 武汉科技大学 Micro-emulsified biological diesel and preparation method thereof
CN102295966A (en) * 2011-07-25 2011-12-28 青岛福瑞斯生物能源科技开发有限公司 Micro-emulsified biodiesel and preparation method thereof
CN102382697A (en) * 2011-10-09 2012-03-21 国家石油石化产品质量监督检验中心(广东) Micro-emulsion biodiesel and preparation method thereof

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