CN101302448A - Blending biodiesel - Google Patents

Blending biodiesel Download PDF

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Publication number
CN101302448A
CN101302448A CNA2008101226796A CN200810122679A CN101302448A CN 101302448 A CN101302448 A CN 101302448A CN A2008101226796 A CNA2008101226796 A CN A2008101226796A CN 200810122679 A CN200810122679 A CN 200810122679A CN 101302448 A CN101302448 A CN 101302448A
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biofuel
oil
mediation
gossypii semen
oleum
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CN101302448B (en
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黄和
谢丽霞
李晓菲
于文涛
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Nanjing Tech University
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/10Biofuels, e.g. bio-diesel
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/20Technologies relating to oil refining and petrochemical industry using bio-feedstock

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  • Fats And Perfumes (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses blending biodiesel, which mainly comprises cottonseed oil biodiesel, tung oil biodiesel and illegal cooking oil biodiesel, and the volume ratio of the cottonseed oil biodiesel to the tung oil biodiesel to the illegal cooking oil biodiesel is 15-35: 10-60: 15-35. The invention has low cost, simple and easy operation process and environmental protection, integrates the advantages of various raw materials of biodiesel and petroleum diesel, and can better improve the performance of the biodiesel.

Description

A kind of mediation biofuel
Technical field
The invention belongs to green, field of renewable energy technology, be specifically related to a kind of optimization biofuel that forms by multiple biofuel mediation.
Background technology
Biofuel is a kind of as green energy resource, has preferably ignition quality and advantage such as renewable, environmentally friendly, becomes the best oil substitutes of prospect.In today of the raising of exhausted day by day and people's environmental consciousness of petroleum resources, biofuel is more and more paid attention to, the emphasis that the development biofuel has become various countries to study.At present, the country that comprises the U.S., European Union, Japan and China is all greatly developing biofuel.Yet, to compare with the relative ripe petrifaction diesel of development, biofuel will realize that also there are some problems inevitably in general commercialization, shows as mainly that raw materials cost height, viscosity are big, easily oxidation and not anti-storage and low-temperature startup performance are good etc.In traditional technology, generally be to mix use with petrifaction diesel, or improve the low-temperature fluidity of biofuel by adding methods such as additive by biofuel.Provide a kind of vegetables oil, additive allotment method of bio-diesel oil utilized as CN1821350A.CN1847369A increases the oxidative stability of biofuel by adding certain particular configuration antioxidant.And the most more complicated of these methods, therefore production cost can't be used so far widely than higher.
The use of biofuel can be divided into this 3 kinds of situations basically: 1. the oiliness additive as petrifaction diesel uses, and generally adding dosage is below 5%; 2. as the blend component of petrifaction diesel, general incorporation is 20%-30%; 3. with Germany the biofuel of the use pure state of representative.At present, most biofuel are used to mix the burning form at coml and are occurred.
Summary of the invention
The objective of the invention is to solve problems such as raw materials cost height in the present biofuel business promotion, viscosity are big, easily the not anti-storage of oxidation and low temperature flowability be not good, provide a kind of use to be in harmonious proportion simply, cheaply and use biofuel.
Purpose of the present invention can reach by following measure:
A kind of mediation biofuel, this mediation mainly is made up of Oleum Gossypii semen biofuel, tung oil biofuel and refining sewer oil biofuel with biofuel, and its volume ratio is 15~35: 10~60: 15~35, be preferably 20~30: 10~50: 20~30.This mediation also can add the Oleum Cocois biofuel with biofuel, wherein the volume ratio between Oleum Cocois biofuel, Oleum Gossypii semen biofuel, tung oil biofuel and the refining sewer oil biofuel is 15~35: 15~35: 10~60: 15~35, be preferably 15~35: 15~35: 10~30: 15~35, most preferably be 20~30: 20~30: 15~20: 20~30.This mediation can also add the rapeseed oil biofuel with biofuel, and wherein the volume ratio of Oleum Cocois biofuel and rapeseed oil biofuel is 15~35: 10~25, is preferably 20~30: 15~20.
It is that 60~98% petrifaction diesel forms mixed oil and uses that this mediation also can be mixed volume content with biofuel, and volume content is 70~90%.
Oleum Cocois biofuel, rapeseed oil biofuel, Oleum Gossypii semen biofuel, tung oil biofuel and refining sewer oil biofuel are raw material with Oleum Cocois, rapeseed oil, Oleum Gossypii semen, tung oil and refining sewer oil respectively, adopt the base-catalyzed transesterification method to make.In the base-catalyzed transesterification process, employed catalyzer is NaOH, and employed low-carbon alcohol is a methyl alcohol, and molar ratio of methanol to oil is 5~20: 1, and temperature of reaction is 30~75 ℃, and the reaction times is 30min~5h.
Concrete technical scheme of the present invention may further comprise the steps:
1) preparation of biofuel
The present invention is the feedstock production biofuel with Oleum Cocois, rapeseed oil, Oleum Gossypii semen, tung oil and refining sewer oil respectively.React the preparation of finishing each raw material biofuel by base-catalyzed transesterification, the usefulness of allotment below after separation, purifying, washing, drying, supplying.The alcohols that uses in the base-catalyzed transesterification reaction is methyl alcohol, catalyzer is highly basic NaOH, best experiment condition is as follows: the preferred alcohols molar equivalent is about 6: 1, the amount of preferred catalyst is that oil is heavy by 1%, the preferred reaction time is about 1-3h, preferable reaction temperature is about 65 ℃, and preferred stirring velocity is about 600rpm.
2) qualitative, the quantitative analysis of each raw material biofuel fatty acid methyl ester composition
Oleum Cocois, rapeseed oil, Oleum Gossypii semen and tung oil all are the abundant vegetable oil materials in source, and sewer oil mainly is the catering trade waste oil of processing through reclaiming, and they all contain a large amount of lipid acid, are the good raw material of preparation biofuel.The present invention adopts GC/MS (gas chromatography mass spectrometry) to being analyzed by the fatty acid methyl ester composition of the biofuel of various feedstock production, and its main component and content are as follows:
A. the composition of each fatty acid methyl ester and content are in the Oleum Cocois biofuel: lauric acid 44.1%, tetradecanoic acid 20.9%, palmitinic acid 11.2%, oleic acid 9.2%, capric acid 5.3%, sad 4.8%, stearic acid 3.3%.
B. the composition of each fatty acid methyl ester and content are in the rapeseed oil biofuel: oleic acid 87.3%, palmitinic acid 6.4%, two ten carbon diluted acid 2.3%, hexadecene acid 1.2%, erucic acid 1.1%, stearic acid 0.77%.
C. the composition of each fatty acid methyl ester and content are in the Oleum Gossypii semen biofuel: linolic acid 56.91%, palmitinic acid 31.2%, stearic acid 5.03%, tetradecanoic acid 3.8%, hexadecene acid 3.15%.
D. the composition of each fatty acid methyl ester and content are in the tung oil oil biodiesel: alpha-ketoacid 71.4%, linolic acid 15.3%, tridecanoic acid 3.8%, pentadecane acid 2.8%, arachidonic acid 1.3%.
E. the composition of each fatty acid methyl ester and content are in the sewer oil biofuel: oleic acid 60.1%, palmitinic acid 24.6%, stearic acid 5.8%, hexadecene acid 3.1%, lauric acid 2.0%, tetradecanoic acid 1.8%, 20 carbon diluted acids 1.3%, arachidonic acid 0.5%, eicosanoic acid 0.5%.
3) the different material biofuel is allocated mutually
At present, biofuel generally is the biofuel of a certain feedstock production and petrifaction diesel blending to be formed mixed oil use in actual applications.The present invention is from the mixture of different raw material biofuel and the angle of petrifaction diesel blending, and the biofuel of research different material is mixed situation earlier, is in harmonious proportion with petrifaction diesel on this basis.
Take all factors into consideration raw materials cost, the carbon chain lengths of biofuel fatty acid methyl ester, factors such as saturated and degree of unsaturation, the biofuel of different material preparation can be allocated according to following different proportion directional:
A. analyze the composition and the content of the biofuel fatty acid methyl ester of respectively originating, as can be seen, unsaturated fatty acids methyl esters content order from high to low is in the different material biofuel: tung oil>rapeseed oil>sewer oil>Oleum Gossypii semen>Oleum Cocois; And the content of saturated fatty acid methyl ester is just in time opposite with unsaturated fatty acid content.Saturated and the degree of unsaturation of fatty acid methyl ester in the biofuel has direct influence to the low-temperature fluidity and the oxidation stability of biofuel.It is reported, when saturated fatty acid content is high in the biofuel, help improving the low-temperature fluidity of biofuel; When the unsaturated fatty acids component content is high in the biofuel, help improving the oxidation stability of biofuel.From coordinating both angles, a kind of preferred proportioning is according to Oleum Cocois: rapeseed oil: Oleum Gossypii semen: tung oil: sewer oil=30: 15: 20: the ratio of 15: 20 (volume ratio) is allocated.
B. rapeseed oil is because the difference in bad border of growth can be divided into high erucic acid type and low erucic acid type.In the used raw material rapeseed oil of the present invention, the content of erucic acid is very low, belongs to low erucic acid type rapeseed oil.Moreover, to using being in great demand of edible oil, cause the price of rapeseed oil to be climbed to a higher point day by day in the market.Consider rapeseed oil to have the difference of type and do not have ubiquity, and the higher factor of Costco Wholesale, in this allotment experiment, do not study.From a kind of preferred proportioning of this angle be according to Oleum Cocois: Oleum Gossypii semen: tung oil: sewer oil=20: 30: 20: the ratio of 30 (volume ratios) is allocated.
C. Oleum Gossypii semen, tung oil, these several non-edible plant oil of sewer oil, there is not the problem of striving grain with the people in cheap than rapeseed oil, these edible oils of Oleum Gossypii semen as the raw material of preparation biofuel.Simultaneously, the unsaturated fatty acid content of Oleum Gossypii semen and sewer oil biofuel is close, about 60%-70%; And the unsaturated fatty acid content of tung oil biofuel has accounted for dominant position.From a kind of preferred proportioning of this angle be according to Oleum Gossypii semen: tung oil: the ratio of sewer oil=25: 50: 25 (volume ratio) is allocated.
4) mediation of biofuel and petrifaction diesel
The biodiesel blend of three kinds of ratio systems is incorporated in the 0# diesel oil with 100%, 30%, 20%, 10%, 0% ratio respectively, forms the mixed oil of three kinds of different ratioss, these several mixed oils are correspondingly represented B100, B30, B20, B10, B0.
5) mensuration of some key property of mixed oil
Abide by that GB/T265 measures respectively and the sulphur content of mixed oil B100, B30, B20, B10 and B0 relatively, the results are shown in Table 1; Abide by that GBT5538-2005 measures respectively and the peroxide value of mixed oil B100, B30, B20, B10 and B0 relatively, the results are shown in Table 2; Abide by that SH/T0248 measures respectively and the cold filter clogging temperature of mixed oil B100, B30, B20, B10 and B0 relatively, the results are shown in Table 3.
The present invention allocates Research on effect mutually by the biofuel that the different material preparation comes, and has solved the some shortcomings that biofuel exists in practical application to a great extent, and the advantage of biofuel is given full play to.The present invention's conception is newer, has reached actual benefit, mainly has the following advantages:
One. the cost aspect:
1) raw materials cost reduces: the present invention utilizes renewable vegetables oil Oleum Cocois, rapeseed oil, Oleum Gossypii semen, tung oil as raw material, and the source of these raw materials is wide; Wherein, the use of Oleum Gossypii semen, tung oil, these several inedible oil of sewer oil has avoided striving with the people problem of grain.Sewer oil can also solve the waste oil problem of catering trade as the raw material of preparation biofuel, has purified emissions.The allotment of different material biofuel is used, and provides convenience for the undue dependence to certain raw material in the biofuel scale operation, has alleviated the restriction that scale operation is influenced by the places of origin of raw materials.
2) production cost reduces: the mutual allotment of biofuel and petrifaction diesel, operating process is simple.By contrast, production technique is simple, reduces production costs.
Two. aspect environmental protection: show that mainly sulphur content is low in the biofuel, make that the discharging of sulfurous gas and sulfide is low; Do not contain the aromatic series alkane that can pollute in the biofuel, thereby waste gas is lower than diesel oil to human body infringement to environment.Therefore, a certain amount of biofuel of admixture is used in mineral diesel, can reach good environmental protection effect.
Three. improve the aspect of performance of biofuel:, can improve the performance of biofuel better by the mutual allotment of different material biofuel and petrifaction diesel.
1) improves oxidation stability: when the content of pure biofuel unsaturated fatty acids is high, oxidized easily; Biofuel peroxide value after the mediation is obviously low than pure biofuel, and is favourable to long storage.
2) improve low-temperature fluidity: the cold filter clogging temperature of mediation artifact diesel oil is lower than petrifaction diesel, and low temperature flowability is better.
Embodiment
The invention will be further described below in conjunction with specific embodiment.
Embodiment 1:
Take by weighing Oleum Gossypii semen 100g in the there-necked flask that has whipping appts, condensation reflux unit and thermometer, place and configure the about 65 ℃ constant temperature water bath apparatus of temperature.Get the NaOH of oil heavily about 1%, be dissolved in the anhydrous methanol, the mol ratio of anhydrous methanol and Oleum Gossypii semen is 6: 1.The anhydrous methanol of dissolving NaOH is mixed with Oleum Cocois, be about the about 2h of stirring reaction under the 600r/min at rotating speed.Change over to after reaction finishes in the separating funnel more than the static 8h, the upper strata is the biofuel crude product.Get upper strata biofuel crude product, evaporate down at 80 ℃ and remove unnecessary methyl alcohol.With the biofuel after the distillation washing evaporation for several times, until the washing water clear.Use anhydrous Na SO at last 4Remove redundant moisture, obtain the biofuel product after the filtration.
The preparation of Oleum Cocois biofuel, rapeseed oil biofuel, tung oil biofuel, sewer oil biofuel is with the Oleum Gossypii semen biofuel.
Embodiment 2:
30 volume parts Oleum Cocois biofuel, 15 volume parts rapeseed oil biofuel, 20 volume parts Oleum Gossypii semen biofuel, 15 volume parts tung oil biofuel and the 20 volume parts sewer oil biofuel of getting embodiment 1 place test tube 1 to carry out thorough mixing.This mixed biologic diesel oil is expressed as B100.The mixed biologic diesel oil of getting in the test tube 1 mixes by blending ratio 30%, 20%, 10%, 0% with mineral diesel respectively, forms mixed oil.Mixed oil correspondingly is expressed as B30, B20, B10, B0.
Abide by the sulphur content that GB380-77 measures mixed oil B100, B30, B20, B10 and B0 respectively; Abide by the peroxide value that GBT5538-2005 measures mixed oil B100, B30, B20, B10 and B0 respectively; Measure the cold filter clogging temperature of mixed oil B100, B30, B20, B10 and B0 respectively in accordance with SH/T0248.The measurement result of its sulphur content, peroxide value, cold filter clogging temperature sees Table 1-3.
Embodiment 3:
20 volume parts Oleum Cocois biofuel, 30 volume parts Oleum Gossypii semen biofuel, 20 volume parts tung oil biofuel and the 30 volume parts sewer oil biofuel of getting embodiment 1 place test tube 2 to carry out thorough mixing.This mixed biologic diesel oil is expressed as B100.The mixed biologic diesel oil of getting in the test tube 2 mixes by blending ratio 30%, 20%, 10%, 0% with mineral diesel respectively, forms mixed oil.Mixed oil correspondingly is expressed as B30, B20, B10, B0.
Abide by the sulphur content that GB380-77 measures mixed oil B100, B30, B20, B10 and B0 respectively; Abide by the peroxide value that GBT5538-2005 measures mixed oil B100, B30, B20, B10 and B0 respectively; Measure the cold filter clogging temperature of mixed oil B100, B30, B20, B10 and B0 respectively in accordance with SH/T0248.
The measurement result of sulphur content, peroxide value, cold filter clogging temperature sees Table 1-3.
Embodiment 4:
25 volume parts Oleum Gossypii semen biofuel, 50 volume parts tung oil biofuel and the 25 volume parts sewer oil biofuel of getting embodiment 1 place test tube 3 to carry out thorough mixing.This mixed biologic diesel oil is expressed as B100.The mixed biologic diesel oil of getting in the test tube 3 mixes by blending ratio 30%, 20%, 10%, 0% with mineral diesel respectively, forms mixed oil.Mixed oil correspondingly is expressed as B30, B20, B10, B0.
Abide by the sulphur content that GB380-77 measures mixed oil B100, B30, B20, B10 and B0 respectively; Abide by the peroxide value that GBT5538-2005 measures mixed oil B100, B30, B20, B10 and B0 respectively; Measure the cold filter clogging temperature of mixed oil B100, B30, B20, B10 and B0 respectively in accordance with SH/T0248.
The measurement result of sulphur content, peroxide value, cold filter clogging temperature sees Table 1-3.
Embodiment 5:
10 volume parts Oleum Cocois biofuel, 10 volume parts rapeseed oil biofuel, 10 volume parts Oleum Gossypii semen biofuel, 10 volume parts tung oil biofuel and the 10 volume parts sewer oil biofuel of getting embodiment 1 place test tube 3 to carry out thorough mixing.This mixed biologic diesel oil is expressed as B100.The mixed biologic diesel oil of getting in the test tube 3 mixes by blending ratio 30%, 20%, 10% with mineral diesel respectively, forms mixed oil.
As can be seen from Table 1, this mediation is obviously low than 0# diesel oil with the sulphur content of biofuel, and well below petrifaction diesel, environment protecting is better to the influence of Air quality in its burning.As can be seen from Table 2, this mediation obviously reduces with the adding along with petrifaction diesel of the peroxide value of biofuel, has improved the oxidation stability of biofuel, and is favourable to its long storage.As can be seen from Table 3, this mediation is lower than 0# diesel oil with the cold filter clogging temperature of biofuel, and low temperature flowability is better.
Each routine sulphur content contrast table of table 1
Figure A20081012267900081
Each routine peroxide value contrast table of table 2
Figure A20081012267900082
Each routine cold filter clogging temperature contrast table of table 3
Figure A20081012267900091

Claims (10)

1, a kind of mediation biofuel is characterized in that this mediation mainly is made up of Oleum Gossypii semen biofuel, tung oil biofuel and refining sewer oil biofuel with biofuel, and its volume ratio is 15~35: 10~60: 15~35.
2, mediation biofuel according to claim 1 is characterized in that this mediation also comprises the Oleum Cocois biofuel with biofuel, and wherein the volume ratio between Oleum Cocois biofuel and the Oleum Gossypii semen biofuel is 15~35: 15~35.
3, mediation biofuel according to claim 2 is characterized in that the volume ratio between described Oleum Cocois biofuel and the Oleum Gossypii semen biofuel is 20~30: 20~30.
4, mediation biofuel according to claim 1 is characterized in that this mediation also comprises the rapeseed oil biofuel with biofuel, and wherein the volume ratio of rapeseed oil biofuel and Oleum Gossypii semen biofuel is 10~25: 15~35.
5, mediation biofuel according to claim 4, the volume ratio that it is characterized in that described rapeseed oil biofuel and Oleum Gossypii semen biofuel is 15~20: 20~30.
6,, it is characterized in that this mediation comprises also that with biofuel volume content is 60~98% petrifaction diesel according to claim 1,2 or 4 described mediation biofuel.
7, mediation biofuel according to claim 6 is characterized in that the volume content that is in harmonious proportion with mineral diesel in the biofuel is 70~90%.
8, according to claim 1,2 or 4 described mediation biofuel, it is characterized in that described Oleum Cocois biofuel, rapeseed oil biofuel, Oleum Gossypii semen biofuel, tung oil biofuel and refining sewer oil biofuel, be raw material with Oleum Cocois, rapeseed oil, Oleum Gossypii semen, tung oil and refining sewer oil respectively, adopt the base-catalyzed transesterification method to make.
9, mediation biofuel according to claim 8 is characterized in that in the base-catalyzed transesterification process that employed catalyzer is NaOH, and employed low-carbon alcohol is a methyl alcohol.
10, mediation biofuel according to claim 8 is characterized in that in the base-catalyzed transesterification process that molar ratio of methanol to oil is 5~20: 1, and temperature of reaction is 30~75 ℃, and the reaction times is 30min~5h.
CN2008101226796A 2008-06-06 2008-06-06 Blending biodiesel Expired - Fee Related CN101302448B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103436303A (en) * 2013-07-23 2013-12-11 济南开发区星火科学技术研究院 B5 biodiesel
WO2023225377A1 (en) * 2022-05-19 2023-11-23 Desmet Belgium Novel process for producing biodiesel with reduced monoacylglycerol content

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1522294B (en) * 2001-07-02 2014-02-19 Sasol技术股份有限公司 Biodiesel-fischer-tropsch hydrocarbon blend

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103436303A (en) * 2013-07-23 2013-12-11 济南开发区星火科学技术研究院 B5 biodiesel
CN103436303B (en) * 2013-07-23 2016-02-03 济南开发区星火科学技术研究院 A kind of B5 biofuel
WO2023225377A1 (en) * 2022-05-19 2023-11-23 Desmet Belgium Novel process for producing biodiesel with reduced monoacylglycerol content

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