CN102796572A - Ultra-clean liquid fuel and preparation method thereof - Google Patents
Ultra-clean liquid fuel and preparation method thereof Download PDFInfo
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- CN102796572A CN102796572A CN2012102585114A CN201210258511A CN102796572A CN 102796572 A CN102796572 A CN 102796572A CN 2012102585114 A CN2012102585114 A CN 2012102585114A CN 201210258511 A CN201210258511 A CN 201210258511A CN 102796572 A CN102796572 A CN 102796572A
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Abstract
The invention discloses an ultra-clean liquid fuel and a preparation method thereof. The ultra-clean liquid fuel is prepared by polyaddition reaction between monohydric alcohol and epoxides and comprises the component of oligomer showed in structural formula I, wherein R1 represents alkyl of C1-C8, R2 represents -H, -CH3 or CH2CH3, and n represents 1-8. The liquid fuel of the present invention is low in toxicity, clean-burning, biodegradable, convenient in storage and transportation. Especially with better oxidation stability and flash point than existing liquid fuels, the liquid fuel of the present invention can be wildly used in gasoline, diesel oil, jet fuel and other fuel fields to replace the existing petroleum, biological liquid fuel and other fuels.
Description
Technical field
The present invention relates to a kind of liquid fuel, particularly a kind of abrasive liquid fuel and preparation method thereof.
Background technology
Fuel can be divided into solid fuel, liquid fuel and geseous fuel by form.Liquid fuel have stable in properties, easily burning, calorific value high, be convenient to transportation and characteristics such as storage, the ash content of coal and pollutant discharge amount are low, mainly comprise crude oil and petroleum product, solar oil, heavy oil, gasoline, kerosene, coal tar, shale oil, synthesize oil product, liquefied coal coil, Aalcohols fuel and other liquid fuels.At present, ore fuel still is in dominant position, but a large amount of exploitations causes ore fuel sources such as coal, oil and natural gas exhausted day by day, even can not keep decades.Along with the world economy fast development of society, demands for energy is also constantly increased, energy problem more and more receives each side and pays close attention to.In recent years, energy prices rose violently, Greenhouse effect aggravate, the energy supply and demand situation constantly worsens, and made energy shortage and environmental problem become the theme of global energy problem.
Given this, both at home and abroad all at the novel liquid fuel of active development, like alcohol fuel, biofuel, alcohol-group fuel, dimethyl ether liquid fuel etc.Wherein, the tempo of alcohol fuel and biofuel is very fast, has obtained the application without degree in countries in the world, solves yet these two kinds of products still exist many bottleneck Technology Needs, still can not large-scale promotion use; Alcohol-group fuel is to be main with methyl alcohol, is mixed with the liquid fuel of polyvalent alcohols such as ethanol, propyl alcohol and alkane, though its anti-knocking property are good, thermo-efficiency is high, cleaning, environmental protection, energy density is low, and calorific value is only at 20-26MJ/kg; The cetane value of dimethyl ether liquid fuel is high, few, the cleaning, of many uses of carbon elements, yet it is a raw material with the Sweet natural gas, has defectives such as non-renewable.
Backward relatively to the exhausted day by day and renewable energy source development technique of fossil resource, cost of development is low, the novel liquid fuel of excellent property has great importance to human development.The present invention carries out the polyreaction generation with monohydroxy-alcohol and epoxide; Develop a kind of novel abrasive liquid fuel---oligo alkylene glycols; It has abrasive, low toxicity, characteristic such as biodegradable; Can be used for fields such as gasoline, diesel oil, boat coal, other fuel, substitute existing liquid petroleum fuel, biological liquid fuel and other fuel.
Summary of the invention
Primary and foremost purpose of the present invention be to the problem that above-mentioned prior art exists provide a kind of low toxicity, combustion cleaning, biodegradable, store liquid fuel of convenient transportation and preparation method thereof; Liquid fuel oxidation stability of the present invention is good; Flash-point is high, has wide range of applications.
In order to achieve the above object, one aspect of the present invention provides a kind of abrasive liquid fuel, and its composition comprises that structural formula is the oligopolymer of I,
Wherein, R
1Be C
1-C
8Alkyl, R
2For-H ,-CH
3Or-CH
2CH
3, n is 1-8.
Particularly, said C
1-C
8Alkyl is straight chained alkyl or branched-chain alkyl, and the average molecular weight range of said formula I oligopolymer is 50-500.
Wherein, said liquid fuel is as gasoline or gasoline component, and its composition comprises that carbonatoms is the formula I oligopolymer of 4-7.
Particularly, said carbonatoms is that the average molecular weight range of the formula I oligopolymer of 4-7 is 50-150.
Wherein, said liquid fuel is as aviation kerosene or aviation kerosene component, and its composition comprises that carbonatoms is the formula I oligopolymer of 8-11.
Particularly, said carbonatoms is that the average molecular weight range of the formula I oligopolymer of 8-11 is 150-240.
Wherein, said liquid fuel is as diesel oil or diesel oil component, and its composition comprises that carbonatoms is the formula I oligopolymer of 12-17.
Particularly, said carbonatoms is that the average molecular weight range of the formula I oligopolymer of 12-17 is 240-500.
The present invention provides a kind of method for preparing above-mentioned abrasive liquid fuel on the other hand, monohydroxy-alcohol and epoxide is carried out polyaddition reaction make said formula I oligopolymer.
Wherein, the carbonatoms of said monohydroxy-alcohol is 1-8, and said epoxide is selected from oxyethane, propylene oxide or butylene oxide ring, and the mol ratio of said monohydroxy-alcohol and epoxide is 1:1-10.
Particularly, said monohydroxy-alcohol is preferably one or more in methyl alcohol, ethanol, the n-propyl alcohol.
Especially; Said monohydroxy-alcohol can be single monohydroxy-alcohol, can be the mixture of multiple monohydroxy-alcohol also, is preferably the mixture of multiple monohydroxy-alcohol; Further be preferably the mixture of methyl alcohol, ethanol, n-propyl alcohol, wherein the volume ratio of methyl alcohol, ethanol, n-propyl alcohol is 6:3:1.
Wherein, said polyaddition reaction is carried out under the katalysis of heteropolyacid salt, and said heteropolyacid salt is selected from one or more in phosphato-molybdic heteropolyacid salt, phospho heteropoly tungstate, silicotungstic heteropolyacid salt, the molybdenum heteropoly tungstic acid salt.
Particularly, the proportioning of the weight of said heteropolyacid salt and said monohydroxy-alcohol and epoxide gross weight is 0.1-1:100.
Especially, the temperature of said polyaddition reaction is 60-120 ℃, is preferably 80 ℃; Absolute pressure is 0.2-0.8MPa, is preferably 0.4MPa; Reaction times is 2-10h, is preferably 6h.
The present invention has the following advantages:
1, the present invention develops a kind of brand-new abrasive liquid fuel, and its preparation technology low in raw material cost simple, easy to operate, that adopted is easy to get, and is easy to realize industrialization production and popularization;
2, liquid fuel of the present invention its compare with existing fuel; Have characteristics such as low toxicity, combustion cleaning, oxidation stability are good, flash-point height; Can be widely used in fields such as gasoline, diesel oil, boat coal and other fuel, to substitute existing oil, biological liquid fuel and other fuel.
Embodiment
Further describe the present invention below in conjunction with specific embodiment, advantage of the present invention and characteristics will be more clear along with description.But these embodiment only are exemplary, scope of the present invention are not constituted any restriction.It will be understood by those skilled in the art that and down can make amendment with form or replace without departing from the spirit and scope of the present invention, but these modifications and replacing all fall in protection scope of the present invention the details of technical scheme of the present invention.
Embodiment 1
Methyl alcohol, ethanol and n-propyl alcohol are mixed according to volume ratio 6:3:1, make alcohol mixture;
Send into reaction kettle after above-mentioned alcohol mixture and propylene oxide mixed, in reaction kettle, add the silicotungstic heteropolyacid sodium catalyst again, carry out polyaddition reaction after mixing; Obtain reaction mixture; The mol ratio of wherein said alcohol mixture and propylene oxide is 1:4, and the proportioning of the weight of catalyzer and alcohol mixture and propylene oxide gross weight is 0.2:100, and the temperature of control polyaddition reaction is 80 ℃; Absolute pressure is 0.4MPa, and the reaction times is 6 hours;
Is 0.01-0.02MPa with above-mentioned reaction mixture in absolute pressure, and temperature is to carry out underpressure distillation under 180-200 ℃, collects 80-90 ℃ cut, and making carbonatoms is the oligosaccharide mixture I of 4-7; Collect 125-135 ℃ cut, making carbonatoms is the oligosaccharide mixture II of 8-11; Collect 180-200 ℃ cut, making carbonatoms is the oligosaccharide mixture III of 12-17;
The quality examination result of oligosaccharide mixture I, II, III sees table 1-3 respectively.
Embodiment 2
Methyl alcohol and ethanol are mixed according to volume ratio 5:5, make alcohol mixture;
Send into reaction kettle after above-mentioned alcohol mixture and oxyethane mixed, in reaction kettle, add the phosphato-molybdic heteropolyacid sodium catalyst again, carry out polyaddition reaction after mixing; Obtain reaction mixture; The mol ratio of wherein said alcohol mixture and oxyethane is 1:8, and the proportioning of the weight of catalyzer and alcohol mixture and oxyethane gross weight is 0.5:100, and the temperature of control polyaddition reaction is 60 ℃; Absolute pressure is 0.6MPa, and the reaction times is 10 hours;
Is 0.01-0.02MPa with above-mentioned reaction mixture in absolute pressure, and temperature is to carry out underpressure distillation under 180-200 ℃, collects 80-90 ℃ cut, and making carbonatoms is the oligosaccharide mixture I of 4-7; Collect 125-135 ℃ cut, making carbonatoms is the oligosaccharide mixture II of 8-11; Collect 180-200 ℃ cut, making carbonatoms is the oligosaccharide mixture III of 12-17;
The quality examination result of oligosaccharide mixture I, II, III sees table 1-3 respectively.
Embodiment 3
With methyl alcohol and alcohol mix according to volume ratio 7:3, make alcohol mixture;
Send into reaction kettle after above-mentioned alcohol mixture and butylene oxide ring mixed, in reaction kettle, add molybdenum heteropoly tungstic acid sodium catalyst again, carry out polyaddition reaction after mixing; Obtain reaction mixture; The mol ratio of wherein said alcohol mixture and butylene oxide ring is 1:2, and the proportioning of the weight of catalyzer and alcohol mixture and butylene oxide ring gross weight is 1:100, and the temperature of control polyaddition reaction is 100 ℃; Absolute pressure is 0.8MPa, and the reaction times is 2 hours;
Is 0.01-0.02MPa with above-mentioned reaction mixture in absolute pressure, and temperature is to carry out underpressure distillation under 180-200 ℃, collects 80-90 ℃ cut, and making carbonatoms is the oligosaccharide mixture I of 4-7; Collect 125-135 ℃ cut, making carbonatoms is the oligosaccharide mixture II of 8-11; Collect 180-200 ℃ cut, making carbonatoms is the oligosaccharide mixture III of 12-17;
The quality examination result of oligosaccharide mixture I, II, III sees table 1-3 respectively.
Embodiment 4
Send into reaction kettle after isopropylcarbinol and propylene oxide mixed, in reaction kettle, add the phosphorus heteropoly tungstic acid sodium catalyst again, carry out polyaddition reaction after mixing; Obtain reaction mixture; The mol ratio of wherein said isopropylcarbinol and propylene oxide is 1:6, and the proportioning of the weight of catalyzer and isopropylcarbinol and propylene oxide gross weight is 0.1:100, and the temperature of control polyaddition reaction is 120 ℃; Absolute pressure is 0.2MPa, and the reaction times is 4 hours;
Is 0.01-0.02MPa with above-mentioned reaction mixture in absolute pressure, and temperature is to carry out underpressure distillation under 180-200 ℃, collects 80-90 ℃ cut, and making carbonatoms is the oligosaccharide mixture I of 4-7; Collect 125-135 ℃ cut, making carbonatoms is the oligosaccharide mixture II of 8-11; Collect 180-200 ℃ cut, making carbonatoms is the oligosaccharide mixture III of 12-17;
The quality examination result of oligosaccharide mixture I, II, III sees table 1-3 respectively.
The quality examination result of table 1 oligosaccharide mixture I
The quality examination result of table 2 oligosaccharide mixture II
| Project | ASTM?D190 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | TP |
| Calorific value MJ/kg | ≥43.5 | 44.3 | 45.1 | 44.8 | 43.9 | D4529 |
| Cetane value | ≥80.7 | 81.6 | 82.1 | 81.9 | 81.2 | D2700 |
| Density g/cm 3 | Report | 0.845 | 0.896 | 0.862 | 0.838 | D1298 |
| Sulphur content % | ≤0.05 | 0.009 | 0.010 | 0.008 | 0.006 | D1266 |
| Flash-point (remaining silent) ℃ | ≥55 | 90 | 88 | 91 | 89 | GB/T261 |
| Oxidation stability (110 ℃) h | ≥25 | 30 | 30 | 30 | 30 | EN14112 |
| Copper corrosion (50 ℃, 3h -1) level | 1 | 1 | 1 | 1 | 1 | D130 |
The quality examination result of table 3 oligosaccharide mixture III
1-3 can know by table:
1, the quality of the carbonatoms 4-7 oligosaccharide mixture I that makes of the present invention meets GB/T17930-2006 motor spirit national standard; The carbonatoms that makes is that the quality of the oligosaccharide mixture II of 8-11 meets ASTMD190 aviation kerosene quality standard; The carbonatoms that makes is that the quality of the oligosaccharide mixture III of 12-17 meets GB/T19147-2003 derv fuel oil national standard; It can be used as gasoline, diesel oil, aviation kerosene or its component and uses, to substitute existing liquid petroleum fuel, biological liquid fuel and other fuel;
2, compare with existing fuel, abrasive liquid fuel of the present invention has low toxicity, combustion cleaning, oxidation stability is good, flash-point is high, store transportation simple, with characteristics such as the rubber packing material consistency is good, be a kind of completely newly and the liquid fuel of excellent property.
Claims (10)
1. abrasive liquid fuel, its composition comprises that structural formula is the oligopolymer of I,
Wherein, R
1Be C
1-C
8Alkyl, R
2For-H ,-CH
3Or-CH
2CH
3, n is 1-8.
2. abrasive liquid fuel as claimed in claim 1 is characterized in that, as gasoline or gasoline component, its composition comprises that carbonatoms is the formula I oligopolymer of 4-7.
3. abrasive liquid fuel as claimed in claim 1 is characterized in that, as aviation kerosene or aviation kerosene component, its composition comprises that carbonatoms is the formula I oligopolymer of 8-11.
4. abrasive liquid fuel as claimed in claim 1 is characterized in that, as diesel oil or diesel oil component, its composition comprises that carbonatoms is the formula I oligopolymer of 12-17.
5. the method for preparing the said abrasive liquid fuel of claim 1 is carried out polyaddition reaction with monohydroxy-alcohol and epoxide and is made described formula I oligopolymer.
6. method as claimed in claim 5 is characterized in that, the carbonatoms of said monohydroxy-alcohol is 1-8, and said epoxide is selected from oxyethane, propylene oxide or butylene oxide ring.
7. like claim 5 or 6 described methods, it is characterized in that the mol ratio of said monohydroxy-alcohol and epoxide is 1:1-10.
8. like claim 5 or 6 described methods, it is characterized in that said polyaddition reaction is carried out under the katalysis of heteropolyacid salt.
9. method as claimed in claim 8 is characterized in that, said heteropolyacid salt is selected from one or more in phosphato-molybdic heteropolyacid salt, phospho heteropoly tungstate, silicotungstic heteropolyacid salt, the molybdenum heteropoly tungstic acid salt.
10. like claim 5 or 6 described methods, it is characterized in that the temperature of said polyaddition reaction is 60-120 ℃, absolute pressure is 0.2-0.8MPa, and the reaction times is 2-10h.
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|---|---|---|---|
| CN2012102585114A CN102796572A (en) | 2012-07-24 | 2012-07-24 | Ultra-clean liquid fuel and preparation method thereof |
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|---|---|---|---|
| CN2012102585114A CN102796572A (en) | 2012-07-24 | 2012-07-24 | Ultra-clean liquid fuel and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103756737A (en) * | 2013-12-26 | 2014-04-30 | 内蒙古金地生物质有限公司 | Bio-based dimethoxyl alkane diesel oil and preparation method thereof |
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| EP2123736A1 (en) * | 2008-05-19 | 2009-11-25 | C.E.-Technology Limited | Method for producing diesel fuels and aviation fuels from C1-C5 alcohols |
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Patent Citations (7)
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| CN1034198A (en) * | 1987-11-06 | 1989-07-26 | 日本触媒化学工业株式会社 | Acid gas absorbent composition |
| CN1093103A (en) * | 1993-03-30 | 1994-10-05 | 姜睿 | The liquid fuel and the preparation method of color flame and fragrance |
| CN1551912A (en) * | 2000-11-08 | 2004-12-01 | Aae������������˾ | Fuel composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103756737A (en) * | 2013-12-26 | 2014-04-30 | 内蒙古金地生物质有限公司 | Bio-based dimethoxyl alkane diesel oil and preparation method thereof |
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Application publication date: 20121128 |