CN102643690B - Improver used for reducing biodiesel freezing point and preparation method thereof - Google Patents
Improver used for reducing biodiesel freezing point and preparation method thereof Download PDFInfo
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- CN102643690B CN102643690B CN201210124911.6A CN201210124911A CN102643690B CN 102643690 B CN102643690 B CN 102643690B CN 201210124911 A CN201210124911 A CN 201210124911A CN 102643690 B CN102643690 B CN 102643690B
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Abstract
The invention discloses an improver used for reducing a biodiesel freezing point and a preparation method thereof. The improver is obtained through copolymerization of a monomer a and monomer b; the mass percent of the monomer a and the monomer b is as follows: the monomer a is 25-45wt% and the monomer b is 55-75wt%; and the number-average molecular weight of the improver is 5000-3000000. Through molecular design, a monomer molecule carrying three crylic acid structural units and stretching three-dimensional space is selected; a three-dimensional macromolecule with a three-dimensional structure when a macromoleclar polymer is formed by polymerization; the three-dimensional macromolecule is stronger in ability than the traditional linear macromolecule combination and adsorption crystal nucleus; and the biodiesel freezing point can be effectively lowered and the low-temperature flowing property is improved.
Description
One, technical field
The present invention relates to additive of a kind of biofuel and preparation method thereof, specifically a kind of improving agent for reducing freezing point of biodiesel and preparation method thereof.
Two, background technology
The mankind can (as oil, coal etc.) be just non-renewable at widely used fossil at present, and in tens of or centuries, these energy will be consumed totally.For example, to the year two thousand twenty, 90% consumption reduction of the prospective oil having been found that is complete, and it is unprecedentedly surging that the severe situation of energy consumption makes to seek the power of new forms of energy.Reproducible biology as wind energy, sun power, bioenergy be the emphasis that people consider.
Biomass energy, as the substitute products of fossil energy, is a kind of reproducible " green energy resource ", and its superiority is apparent.As can newly do not produced carbonic acid gas in carbon cycle, thus can newly not produce greenhouse gases, thereby can alleviate Greenhouse effect; Biodegradable determines that it is environmentally friendly; Use biomass energy also to contribute to control of acid rain and airborne particulate emission.An important representative of biomass energy is biofuel, and natural fats and oils reacts the product fatty acid ester obtaining with alcohol compound.Biofuel, as the substitute products of gasoline or petrifaction diesel, is entering the early stage of extensive development.An environment-friendly advantage of biofuel is that it can reduce engine exhaust discharge.Biofuel does not almost have sulfur compound, and the waste gas of discharge does not have sulfide naturally yet.Comprise that the important country in the world of the U.S., Japan, China is to biofuel exploitation great attention.
Yet biofuel is compared with petrifaction diesel, its zero pour and viscosity are relatively high.The zero pour of petrifaction diesel is greatly about subzero 15 ℃, and biofuel just can start to solidify when the temperature of 0 ℃ even higher, is easy to stop up automobile oil-way during low temperature.In winter, use biofuel must add additive or other Insulation.
The ester that EP691355 has described the alkoxylated alcohol of take methyl-prop diluted acid and containing ethylene oxy unit with dissemination is basic polymkeric substance, can be for the dispersion agent in lubricating oil.Its molecular weight is 1000 to 300000 dalton.
DE19751501.0 has reported a kind of additive of biofuel, and the polymkeric substance being formed by three kinds of monomer polymerizations has the effect of the zero pour that reduces biofuel.
Yet what reported at present is linear structure for improving the high molecular polymer overwhelming majority of biodiesel lower-temperature fluidity, i.e. linear macromolecule.And macromolecular compound acts on biofuel to make its depression of the freezing point principle is to utilize the space structure of macromolecular compound, be adsorbed on around nucleus, stop the further growth of nucleus, thereby reach the object that improves biodiesel lower-temperature fluidity.From macromolecular structure, the three-dimensional polymeric molecule with three-dimensional arrangement has larger superiority than linear macromolecule.
Three, summary of the invention
The present invention aims to provide a kind of improving agent for reducing freezing point of biodiesel and preparation method thereof, and technical problem to be solved is the low temperature flowability that reduces the zero pour of biofuel and improve biofuel.
The present invention passes through molecular designing, select the monomer molecule that carries three acrylic acid structure unit and stretch to three-dimensional space, when forming high molecular polymer, polymerization forms the three-dimensional polymeric molecule with 3-D solid structure, ability than traditional linear macromolecule combination and absorption nucleus is stronger, can more effectively reduce freezing point of biodiesel, improve its low temperature flowability.
The present invention, for reducing the improving agent of freezing point of biodiesel, is characterized in that: the improving agent being obtained by copolyreaction by monomer a and monomer b; Monomer a and monomer b are configured to by mass percentage: monomer a 25-45wt%, and surplus is monomer b; The number-average molecular weight of described improving agent is 5000-3000000;
The structural formula of described monomer a is represented by general formula (I):
N=1-15 wherein;
The structural formula of described monomer b is represented by general formula (II):
R wherein
1for the alcohol that carbonatoms is 1-18, can be straight chain alcohol or branched alcohol.
Preferred n=1 in general formula (I), monomer a is Viscoat 295.
The present invention is for reducing the preparation method of the improving agent of freezing point of biodiesel, it is characterized in that: under the existence of nitrogen protection and solvent, the monomer b of the monomer a of 30wt% and 30wt% is added in reactor, the addition of solvent is 0.1-2 times of monomer total mass, add subsequently initiator, be warming up to 60-80 ℃ of reaction 2-4 hour, then add the monomer a of surplus and the monomer b of surplus, be warming up to 120-140 ℃ of reaction 3-4 hour, after reaction finishes, add rapeseed oil to dilute and stir, the volume 1-2 that the add-on of rapeseed oil is described solvent doubly;
Initiator and 12 carbon alkyl sulfhydryls can be added in reactor in the lump in addition, the addition of 12 carbon alkyl sulfhydryls is the 1-2% of monomer total mass.
Described initiator is selected from ammonium peroxydisulfate, Potassium Persulfate, benzoyl peroxide, Diisopropyl azodicarboxylate, isopropyl benzene hydroperoxide, t-butyl hydrogen peroxide, dicumyl peroxide, azo-bis-iso-dimethyl, crosses PIVALIC ACID CRUDE (25) tertiary butyl fat, crosses different n-nonanoic acid tertiary butyl fat, crosses one or more in sad tertiary butyl fat, and initiator amount is the 0.2-4% of monomer total mass.
Described solvent is selected from organic solvent or water, and described organic solvent is selected from toluene, benzene, dimethylbenzene, normal hexane, sherwood oil, methyl-sulphoxide, alcohols, hexanodioic acid two (2-ethyl diethyldithiocarbamate) ester or natural fats and oils.
Improving agent prepared by the present invention adds in biofuel to reduce its zero pour and to improve its low temperature flowability, the 0.05-5wt% that the addition of improving agent of the present invention is biological diesel quality.
Compared with the prior art, beneficial effect of the present invention is embodied in:
The present invention passes through molecular designing, select the monomer molecule that carries three acrylic acid structure unit and stretch to three-dimensional space, when forming high molecular polymer, polymerization forms the three-dimensional polymeric molecule with 3-D solid structure, ability than traditional linear macromolecule combination and absorption nucleus is stronger, can more effectively reduce freezing point of biodiesel, improve its low temperature flowability.
Four, embodiment
Below by embodiment, the present invention is further set forth:
Embodiment 1:
In a 2000mL reaction unit with electric mixer, thermometer, reflux exchanger, nitrogen ingress pipe, under the condition of logical nitrogen, add 200mL hexanodioic acid two (2-ethyl diethyldithiocarbamate) ester, 12 carbon alkyl sulfhydryl 6g, Viscoat 295 45g, vinylformic acid 2-hydroxyl ethyl ester 105g and cross sad tertiary butyl ester 20g, stir and be heated to 60 ℃, reacting 2 hours; Then in reaction solution, add Viscoat 295 105g and vinylformic acid 2-hydroxyl ethyl ester 245g, be warming up to subsequently 120-140 ℃, react 4 hours, after reaction finishes, add 200mL rapeseed oil to dilute and stir to be improving agent.。
Embodiment 2:
In a 2000mL reaction unit with electric mixer, thermometer, reflux exchanger, nitrogen ingress pipe, under the condition of logical nitrogen, add 400mL hexanodioic acid two (2-ethyl diethyldithiocarbamate) ester, Viscoat 295 37.5g, vinylformic acid 2-hydroxypropyl acrylate 112.5g and t-butyl hydrogen peroxide 20g, stir and be heated to 70 ℃, reacting 3 hours; Then in reaction solution, add Viscoat 295 87.5g and vinylformic acid 2-hydroxypropyl acrylate 262.5g, be warming up to subsequently 120 ℃, react 4 hours, after reaction finishes, add 400mL rapeseed oil to dilute and stir to be improving agent.。
Embodiment 3:
In a 2000mL reaction unit with electric mixer, thermometer, reflux exchanger, nitrogen ingress pipe, under the condition of logical nitrogen, add 100mL hexanodioic acid two (2-ethyl diethyldithiocarbamate) ester, Viscoat 295 67.5g, vinylformic acid 2-hydroxyl second fat 82.5g and cross different n-nonanoic acid tertiary butyl ester 20g, stir and be heated to 80 ℃, reacting 4 hours; Then in reaction solution, add Viscoat 295 157.5g and vinylformic acid 2-hydroxyl ethyl ester 192.5g, be warming up to subsequently 130 ℃, react 4 hours, after reaction finishes, add 150mL rapeseed oil to dilute and stir to be improving agent.
Claims (6)
1. for reducing an improving agent for freezing point of biodiesel, it is characterized in that: the improving agent being obtained by copolyreaction by monomer a and monomer b; Monomer a and monomer b are configured to by mass percentage: monomer a25-45wt%, and surplus is monomer b; The number-average molecular weight of described improving agent is 5000-3000000;
The structural formula of described monomer a represents by leading to formula I:
N=1-15 wherein;
The structural formula of described monomer b represents by leading to formula II:
R wherein
1for the carbonatoms alcohol that is 1-18;
Described improving agent is the improving agent preparing by the following method:
Under the existence of nitrogen protection and solvent, the monomer b of the monomer a of 30wt% and 30wt% is added in reactor; the addition of solvent is 0.1-2 times of monomer total mass; add subsequently initiator; be warming up to 60-80 ℃ of reaction 2-4 hour; then add the monomer a of surplus and the monomer b of surplus; be warming up to 120-140 ℃ of reaction 3-4 hour, reaction adds rapeseed oil to dilute after finishing and stirs and obtain improving agent.
2. the improving agent for reducing freezing point of biodiesel according to claim 1, is characterized in that: n=1 in logical formula I, monomer a is Viscoat 295.
3. the preparation method of the improving agent for reducing freezing point of biodiesel claimed in claim 1, it is characterized in that: under the existence of nitrogen protection and solvent, the monomer b of the monomer a of 30wt% and 30wt% is added in reactor, the addition of solvent is 0.1-2 times of monomer total mass, add subsequently initiator, be warming up to 60-80 ℃ of reaction 2-4 hour, then add the monomer a of surplus and the monomer b of surplus, be warming up to 120-140 ℃ of reaction 3-4 hour, after reaction finishes, add rapeseed oil to dilute and stir, the add-on of rapeseed oil is 1-2 times of described solvent volume,
Described initiator is selected from ammonium peroxydisulfate, Potassium Persulfate, benzoyl peroxide, Diisopropyl azodicarboxylate, isopropyl benzene hydroperoxide, t-butyl hydrogen peroxide, dicumyl peroxide, azo-bis-iso-dimethyl, crosses PIVALIC ACID CRUDE (25) tertiary butyl fat, crosses different n-nonanoic acid tertiary butyl fat, crosses one or more in sad tertiary butyl fat, and initiator amount is the 0.2-4% of monomer total mass.
4. preparation method according to claim 3, is characterized in that: initiator and 12 carbon alkyl sulfhydryls are added in reactor in the lump, and the addition of 12 carbon alkyl sulfhydryls is the 1-2% of monomer total mass.
5. according to the preparation method described in claim 3 or 4, it is characterized in that: described solvent is selected from organic solvent or water.
6. preparation method according to claim 5, is characterized in that: described organic solvent is selected from toluene, benzene, dimethylbenzene, normal hexane, sherwood oil, methyl-sulphoxide, hexanodioic acid two (2-ethyl diethyldithiocarbamate) ester, alcohols or natural fats and oils.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107384491A (en) * | 2017-08-01 | 2017-11-24 | 安徽工程大学 | A kind of preparation method of high-efficiency diesel pour inhibitor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104017655A (en) * | 2013-03-03 | 2014-09-03 | 河源市汇盛生物科技有限公司 | Method for reducing solidifying point of biodiesel |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102120804A (en) * | 2009-12-21 | 2011-07-13 | 英菲诺姆国际有限公司 | Improvements in polymers |
| EP2305753B1 (en) * | 2009-09-25 | 2012-02-29 | Evonik RohMax Additives GmbH | A composition to improve cold flow properties of fuel oils |
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| AU2005231958B2 (en) * | 2004-04-06 | 2010-04-01 | Akzo Nobel Chemicals International B.V. | Pour point depressant additives for oil compositions |
| US8349033B2 (en) * | 2007-05-31 | 2013-01-08 | The Penray Companies, Inc. | Diesel fuel, diesel fuel additive, and associated method for using the same |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2305753B1 (en) * | 2009-09-25 | 2012-02-29 | Evonik RohMax Additives GmbH | A composition to improve cold flow properties of fuel oils |
| CN102120804A (en) * | 2009-12-21 | 2011-07-13 | 英菲诺姆国际有限公司 | Improvements in polymers |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107384491A (en) * | 2017-08-01 | 2017-11-24 | 安徽工程大学 | A kind of preparation method of high-efficiency diesel pour inhibitor |
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