CN101353600A - Biodiesel antioxidant and biodiesel containing the same - Google Patents
Biodiesel antioxidant and biodiesel containing the same Download PDFInfo
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- CN101353600A CN101353600A CNA2008100423778A CN200810042377A CN101353600A CN 101353600 A CN101353600 A CN 101353600A CN A2008100423778 A CNA2008100423778 A CN A2008100423778A CN 200810042377 A CN200810042377 A CN 200810042377A CN 101353600 A CN101353600 A CN 101353600A
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Abstract
The invention relates to a biodiesel antioxidant and a biodiesel containing the biodiesel antioxidant. The invention discloses a biodiesel antioxidant which can be compounds with the following structural general formula (I) or an arbitrary mixture thereof. The biodiesel antioxidant disclosed by the invention can obviously increase the oxidative stability of the biodiesel and greatly improve the quality of the biodiesel; furthermore, the antioxidant has low price and low addition amount, thus effectively prolonging the service life of the oil. Simultaneously, the added antioxidant has no obvious influence on other physicochemical properties of the biodiesel.
Description
Technical field
The present invention relates to a kind of biological diesel oil antioxidant agent and contain its biofuel.
Background technology
Biofuel is a kind of fine diesel oil substitute; have outstanding environment friendly and recyclability; development biofuel industry is for ensureing Oil Safety, preserve the ecological environment, promote agriculture production and realizing that Sustainable development all has crucial meaning.In recent years, the research of biofuel makes a breakthrough, and one is that the emerging renewable energy source industry of representative just at home and abroad is surging forward with the biofuel.
Biofuel is to be raw material with oil-containing animal-plant oil, waste grease, engineering algae etc., with the fatty acid methyl ester that methyl alcohol is made by transesterification reaction, is a kind of reproducible cleaning oxygen-bearing liquid fuel.
Because biofuel generally contains more unsaturated fatty acids methyl esters, as Witconol 2301, methyl linoleate, Linolenic acid methylester etc., compare with petrifaction diesel, the biofuel less stable, be very easy to deterioration by oxidation, ageing products such as the insoluble and soluble polymer that oxidation generates, aging acid and superoxide can cause the engine filter screen to stop up and the squirt pump coking, cause smoke evacuation to increase, start difficulty, flame-out; Cause aging the becoming fragile of engine metal component corrosion, rubber components and cause use problems such as fuel leakage, the fuel that has a strong impact on the normal use of biofuel in self-igniton engine can value.Therefore, in China's " diesel-fuel blending biofuel (BD100) " standard GB/T20828-2007 technical requirements, oxidation stability index to biofuel has strict regulation, requirement is under 110 ℃ of promote the oxidation conditions, and the oxidation stability of biofuel can not be lower than 6 hours.At present, China most of production of biodiesel enterprise is raw materials used to be high acid value raw materials such as waste animal and vegetable oil, acidifying oil, swill oil, cause the oxidation stability index of biofuel finished product to be difficult to the requirement that is up to state standards, this just need take certain technique means to improve the oxidative stability of biofuel, to improve the quality of biofuel.
According to prior art, by adding the method for chemical antioxidants, can obtain the biofuel that oxidation stability has improved.Chinese patent application number is to have described in 03825109.4 the patent to adopt 2, and 4-di-t-butyl hydroxy toluene (BHT) antioxidant improves the method for storage stability of bio-diesel, but the additive capacity of antioxidant is higher, has increased use cost; Application number is 200510137575.9 patent increases biofuel by main antioxidant and the composite method of secondary antioxidant a oxidative stability, but main antioxidant and secondary antioxidant chemical structure relative complex, synthetic cost is higher, and use is restricted.
Summary of the invention
That technical problem to be solved by this invention is is certain density by adding, the simple relatively antioxidant of structure and (or) other additives, solve the relevant antioxidant of forefathers and add the higher defective of cost, and improved the oxidation stability of biofuel.
On the one hand, the invention discloses a kind of biological diesel oil antioxidant agent, this antioxidant is for having the compound of following general structure (I) or their any mixture
Wherein, R
1For-H or-CH
3Or-C (CH
3)
3
R
2For-H or-OH or-(CH
2)
2COO-i-C
nH
2n+1, wherein n is 1～10, is preferably
4～8
R
3For-H or-CH
3Or-C (CH
3)
3
R
4For-H or-CH
3Or-C (CH
3)
3
In an embodiment, described antioxidant is selected from 2,6-di-tert-butyl hydroquinone, 2,5-di-tert-butyl hydroquinone, 2, one of in 6-di-tert-butyl methyl phenol, four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester or β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid isooctyl alcohol ester or their any mixture, wherein be preferably 2, the 6-di-tert-butyl hydroquinone.
On the other hand, the present invention also discloses a kind of biofuel that contains antioxidant of the present invention, and the content of wherein said antioxidant is 50～5000ppm.Ppm represents the weight of contained solute in the solution of 1,000,000 parts of weight.
The oxidation mechanism of biofuel is the chain reaction of free radical, comprises chain initiation, chainpropagation and three reaction process of chain termination.Add the main anti-oxidant free radical of can directly dieing out, the free radical quantity in the reaction system is reduced rapidly, free chain reaction stops, thereby the protection biofuel is avoided oxidation and destroyed.
Above-mentioned antioxidant can directly be added in the biofuel according to additive capacity with the solid form, heats under 40 ℃～80 ℃ conditions, is stirred to antioxidant and is dissolved in fully and treats in the stable biofuel.
Above-mentioned antioxidant also can be dissolved in earlier and treat in the stable biofuel, is mixed with concentration and is 5%～40% mother liquor, reaches 50～5000ppm until antioxidant concentration.
Described biofuel is the fatty acid methyl ester that vegetable and animals oils fat raw material and alcohols prepare by transesterification reaction, and described vegetable and animals oils fat raw material is rapeseed oil, soybean oil, waste cooking oil, sewer oil, Oleum Gossypii semen, plam oil, Fructus Zanthoxyli oil, barbadosnut seed oil, rice bran wet goods; Described alcohols is a methyl alcohol.
Can add other conventional oil dope in the described biofuel, as low temperature flow promoter (pour point depressant), metal passivator and sterilant etc.
Biological diesel oil antioxidant agent disclosed in this invention can significantly increase the oxidation stability of biofuel, improve the quality quality of biofuel widely, and described antioxidant is cheap, add-on is low, can effectively prolong oil product work-ing life.Simultaneously, the oxidation inhibitor of interpolation does not have obvious influence to other physico-chemical property of biofuel.
Embodiment
For technique means, creation characteristic that the present invention is realized, reach purpose and effect is easy to understand, below in conjunction with concrete diagram, further set forth the present invention.
The biodiesel manufacture reaction formula is
The used catalyzer of preparation process can be acid, alkali or biological enzyme.
The mensuration of oxidation stability of biodiesel
According to the standard EN 14112:2003 of European Union, grease derivative-fatty acid methyl ester: oxidation stability test method (promote the oxidation method), used instrument are Switzerland's ten thousand logical 873 biofuel oxidative stability determinators (Metrohm 873 Biodiesel Rancimat).
Biofuel generates volatile acid secondary oxidative product under heating, logical oxygen promote the oxidation condition, brought in the cuvette that deionized water is housed by the airflow that feeds.Measure the variation of deionized water specific conductivity in the cuvette by conductance electrode, by workstation software automatically to electricity lead-time curve carries out quadratic integral, provides maximum value, is the induction time of biofuel, with a hour expression.The oxidation stability of representing biofuel with induction time.
Take by weighing about 3.0g from the biofuel sample (being accurate to 0.01g) of different material preparation in reaction tubes, under 110 ℃ of test temperatures, air flow quantity 10L/h condition, the induction time of working sample generation promote the oxidation.
Embodiment 1
Oxidation induction time 1.51h when not adding any antioxidant in the rapeseed oil biofuel; Adding concentration in the rapeseed oil biofuel is the oxidation inhibitor 2 of 250ppm, and the 6-di-tert-butyl hydroquinone is 60 ℃ of following stirring and dissolving in temperature, and what obtain clear treats stabilate diesel oil solution.According to the standard EN 14112:2003 of European Union method, the induction time of working sample under 110 ℃ of temperature is 20.23h.
Embodiment 2
Adding concentration in the rapeseed oil biofuel is the oxidation inhibitor 2 of 50ppm, and the 6-di-tert-butyl hydroquinone is 60 ℃ of following stirring and dissolving in temperature, and what obtain clear treats stabilate diesel oil solution.According to the standard EN 14112:2003 of European Union method, the induction time of working sample under 110 ℃ of temperature is 6.20h.
Embodiment 3
Adding concentration in the rapeseed oil biofuel is the oxidation inhibitor 2 of 5000ppm, and the 6-di-tert-butyl hydroquinone is 80 ℃ of following stirring and dissolving in temperature, and what obtain clear treats stabilate diesel oil solution.According to the standard EN 14112:2003 of European Union method, the induction time of working sample under 110 ℃ of temperature is 37.55h.
Embodiment 4
Adding concentration in the rapeseed oil biofuel is the oxidation inhibitor 2 of 500ppm, and the 5-di-tert-butyl methyl phenol is 80 ℃ of following stirring and dissolving in temperature, and what obtain clear treats stabilate diesel oil solution.According to the standard EN 14112:2003 of European Union method, the induction time of working sample under 110 ℃ of temperature is 7.04h.
Embodiment 5
Adding concentration in the rapeseed oil biofuel is oxidation inhibitor four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester of 500ppm, is 50 ℃ of following stirring and dissolving in temperature, and what obtain clear treats stabilate diesel oil solution.According to the standard EN 14112:2003 of European Union method, the induction time of working sample under 110 ℃ of temperature is 7.80h.
From above five embodiment, the oxidation stability that the oxidation stability that has added the rapeseed oil biofuel of antioxidant is not added the rapeseed oil biofuel of antioxidant has improved greatly.
Embodiment 6
The oxidation induction time that the sewer oil biofuel is not added antioxidant is 2.55h.Adding concentration in the sewer oil biofuel is the oxidation inhibitor 2 of 500ppm, and the 6-di-tert-butyl hydroquinone is 70 ℃ of following stirring and dissolving in temperature, and what obtain clear treats stabilate diesel oil solution.According to the standard EN 14112:2003 of European Union method, the induction time of working sample under 110 ℃ of temperature is 18.06h.
Embodiment 7
Adding concentration in the sewer oil biofuel is the oxidation inhibitor 2,5 di tert butyl hydroquinone of 1000ppm, is 50 ℃ of following stirring and dissolving in temperature, and what obtain clear treats stabilate diesel oil solution.According to the standard EN 14112:2003 of European Union method, the induction time of working sample under 110 ℃ of temperature is 9.92h.
From above two embodiment, the oxidation stability that the oxidation stability that has added the sewer oil biofuel of antioxidant is not added the sewer oil biofuel of antioxidant has improved greatly.
Embodiment 8
The oxidation induction time that the Fructus Zanthoxyli oil biofuel is not added antioxidant is 1.17h; Adding concentration in the Fructus Zanthoxyli oil biofuel is the oxidation inhibitor 2 of 1000ppm, and the 6-di-tert-butyl hydroquinone is 80 ℃ of following stirring and dissolving in temperature, and what obtain clear treats stabilate diesel oil solution.According to the standard EN 14112:2003 of European Union method, the induction time of working sample under 110 ℃ of temperature is 9.27h.
From embodiment 8 as can be seen, the oxidation stability that has added the Fructus Zanthoxyli oil biofuel of the antioxidant oxidation stability of not adding the Fructus Zanthoxyli oil biofuel of antioxidant has improved greatly.
Embodiment 9
The oxidation induction time that the plam oil biofuel is not added antioxidant is 2.38h; Adding concentration in the plam oil biofuel is the oxidation inhibitor 2 of 100ppm, and the 6-di-tert-butyl hydroquinone is 60 ℃ of following stirring and dissolving in temperature, and what obtain clear treats stabilate diesel oil solution.According to the standard EN 14112:2003 of European Union method, the induction time of working sample under 110 ℃ of temperature is 12.51h.
From embodiment 9 as can be seen, the oxidation stability that has added the plam oil biofuel of the antioxidant oxidation stability of not adding the plam oil biofuel of antioxidant has improved greatly.
More than show and described ultimate principle of the present invention, principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; that describes in the foregoing description and the specification sheets just illustrates principle of the present invention; the present invention also has various changes and modifications without departing from the spirit and scope of the present invention, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (6)
1. biological diesel oil antioxidant agent, this antioxidant is for having the compound of following general structure (I) or their any mixture
Wherein, R
1For-H or-CH
3Or-C (CH
3)
3
R
2For-H or-OH or-(CH
2)
2COO-i-C
nH
2n+1, wherein n is 1～10
R
3For-H or-CH
3Or-C (CH
3)
3
R
4For-H or-CH
3Or-C (CH
3)
3
2. biological diesel oil antioxidant agent as claimed in claim 1 is characterized in that described R
2For-(CH
2)
2COO-i-C
nH
2n+1, wherein n is 4～8.
3. biological diesel oil antioxidant agent as claimed in claim 1, it is characterized in that described biological diesel oil antioxidant agent is selected from 2,6-di-tert-butyl hydroquinone, 2,5-di-tert-butyl hydroquinone, 2,6-di-tert-butyl methyl phenol, four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] one of in pentaerythritol ester or β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid isooctyl alcohol ester or their any mixture.
4. biological diesel oil antioxidant agent as claimed in claim 3 is characterized in that described biological diesel oil antioxidant agent is 2, the 6-di-tert-butyl hydroquinone.
5. the biofuel that contains each described biological diesel oil antioxidant agent of claim 1-4.
6. biofuel as claimed in claim 5, the content that it is characterized in that described biological diesel oil antioxidant agent is 50～5000ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100423778A CN101353600A (en) | 2008-09-02 | 2008-09-02 | Biodiesel antioxidant and biodiesel containing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100423778A CN101353600A (en) | 2008-09-02 | 2008-09-02 | Biodiesel antioxidant and biodiesel containing the same |
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|---|---|
| CN101353600A true CN101353600A (en) | 2009-01-28 |
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013062840A1 (en) | 2011-10-28 | 2013-05-02 | Exxonmobil Research And Engineering Company | Dye-stable biofuel blend compositions |
| CN110358084A (en) * | 2019-07-31 | 2019-10-22 | 浙江大学 | A kind of polyethyleneimine amine macromolecular antioxidant and application that hindered phenol is modified |
-
2008
- 2008-09-02 CN CNA2008100423778A patent/CN101353600A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013062840A1 (en) | 2011-10-28 | 2013-05-02 | Exxonmobil Research And Engineering Company | Dye-stable biofuel blend compositions |
| CN110358084A (en) * | 2019-07-31 | 2019-10-22 | 浙江大学 | A kind of polyethyleneimine amine macromolecular antioxidant and application that hindered phenol is modified |
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Application publication date: 20090128 |