CN101082004A - Biological diesel modifying agent and preparation method thereof - Google Patents
Biological diesel modifying agent and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to one kind of biodiesel oil modifier and its preparation process. The biodiesel oil modifier is compounded with antioxidant 1-10 weight portions, antioxidant synergist 0-5 weight portions, biodiesel oil of rape seed oil 50-100 weight portions, and low temperature flow improver 5-50 weight portions. The biodiesel oil modifier can raise the stability of biodiesel oil and improve its low temperature flow performance effectively, and has convenient use, wide adaptability, long storage period, capacity of being used in low temperature and low cost.
Description
Technical field
The present invention relates to a kind ofly be used to improve oxidation stability of biodiesel and improve biological diesel modifying agent of low temperature flowability and preparation method thereof, this modifying agent can effectively prolong biofuel oxidation induction period (IP value, 110 ℃, h), obviously reduce its cold filter clogging temperature (CFPP, ℃), belong to oil chemistry and Application in Chemical Engineering field.
Background technology
Biofuel is to be raw material with animal oil, vegetables oil, discarded edible wet goods, carries out the fatty acid alkyl ester mixture that transesterification reaction obtains under certain condition with low-carbon alcohol, is fatty acid methyl ester admixture generally speaking.Biofuel has environmental friendliness, feature such as biodegradable and renewable, is the favorable substitutes and the important supplement of petrifaction diesel.But compare with petrifaction diesel, the oxidation stability of biofuel is relatively poor, thereby has limited the unsaturated fatty acid ester especially content of high unsaturated fatty acid ester in biofuel and the popularity in biodiesel raw material source.Simultaneously, during biofuel generation autoxidation, can produce a large amount of secondary oxidation products, comprise the oligopolymer of aldehyde, ketone, short chain carboxy acid and higher molecular weight etc., therefore produce precipitation and cause the biofuel muddiness, reduce the biofuel calorific value, the acidic substance of generation are easy to corrode metal partss such as the system that sprays into, pump, nozzle of diesel motor, the polymkeric substance that oxidation produces may cause the engine filter screen to stop up and the squirt pump coking, produces insoluble incrustation.In addition, incomplete combustion also may take place and causes carbon deposit and black smoke in these oxidation productss.Therefore, as will improving its oxidation stability with this renewable energy source of biofuel as power fuel.
US 2004/0139649 A1 and CN 1742072A have described with 3,5-di-t-butyl-4-hydroxytoluene (BHT) improves the method for storage stability of bio-diesel, this method will contain the liquid stoste of BHT that 10%～60% (w/w) in stoste be dissolved in biofuel and join in the biofuel, in total solution of biofuel, the content of BHT reaches 0.005%～2% (w/w).
The described modifying agent of this patent only is used to improve oxidation stability of biodiesel, and this patent is not tested the IP value of adding antioxidant artifact diesel oil, but has measured the changing conditions of its unsaturated fatty acid content.
Can the flowing property of biofuel under cold condition not only is related to the diesel motor fuel plenum system at low temperatures normal fuel injection, and with operations such as at low temperatures storage of biofuel, transportation, loading and unloading substantial connection be arranged all normally.Similar with petrifaction diesel, the crystallization of power fuel component also can appear in biofuel when low temperature, and biofuel is heavier than 0# diesel oil distillate, and viscosity is bigger, and its low temperature crystallization and gel phenomenon are unfavorable for that biofuel uses under cold condition.The raw material sources difference, the low temperature flowability of biofuel shows than big-difference.By add a small amount of cold flow improver in biofuel is an effective way improving its low-temperature performance.The same with petrifaction diesel, the low temperature flowability of biofuel is generally used cloud point (Cloud Point, CP), cold filter clogging temperature (Cold Filter Plugging Point, CFPP), condensation point (Solidifying Point, SP), (Pour Point PP) waits and weighs pour point, wherein the actual use temperature of cold filter clogging temperature and fuel has good corresponding relation, use has actual directive significance to biodiesel fuel, therefore, weighs the low temperature flowability of biofuel with cold filter clogging temperature.
CN 1279707A has described the additive that is used to improve biofuel and biofuel oil low-temperature fluidity that the multipolymer by methacrylic ester constitutes.Add this additive of different concns, the biofuel cold filter clogging temperature is reached below-20 ℃, can obtain preferably pour point simultaneously and solidify point value.This additive only is used to improve the biodiesel lower-temperature fluidity energy, and function is comparatively single.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of comprehensive biological diesel modifying agent that improves performance and preparation method thereof that has at the deficiency of above-mentioned prior art existence, it can not only improve the oxidation stability of biofuel, and can improve the biodiesel lower-temperature fluidity energy, and strengthened the improve effect of modifying agent to biodiesel quality.
The present invention for the technical scheme that problem adopted of the above-mentioned proposition of solution is:
Formed by antioxidant, anti-oxidant synergistic agent, rapeseed oil biofuel (RME) and cold flow improver mixed preparing, each component concentration is by weight: 1～10 part of antioxidant, 0～5 part of anti-oxidant synergistic agent, 50～100 parts of rapeseed oil biofuel (RME), 5～50 parts of cold flow improvers.
Described antioxidant is fat-soluble strong antioxidant, comprise tertiarybutylhydroquinone (TBHQ), 3,5-di-t-butyl-4-hydroxytoluene (BHT), 3-tertiary butyl-4-hydroxy-phenylmethylether (BHA) or vitamin-E (VE), can also comprise 3,5-di-t-butyl-4-hydroxyl-phenylmethylether (Topanol), dihydroguaiaretic acid (NDGA), guaiac(um) (RG), 2 fall, 4,5-trihydroxy--propylbenzene ketone (THBP), 4-methylol-2,6-DI-tert-butylphenol compounds or 6-oxyethyl group-1,2-dihydro-2,2,4-trimethylammonium Kui quinoline.
Described anti-oxidant synergistic agent is L-Quicifal (AP), phytic acid, phosphatide, can also be citric acid, tartrate.Add the anti-oxidation efficacy that anti-oxidant synergistic agent can further strengthen modifying agent.
In the above-mentioned antioxidant, BHA and BHT are used in combination better than single use antioxidant effect, its portfolio ratio generally with 1: 1 for well, add synergistic agent AP better effects if after BHA, BHT are composite again; TBHQ is better than the independent result of use of TBHQ with the composite use of VE, AP.Composite use can strengthen improved effect, reduces addition and reduces the interpolation cost.
Described cold flow improver is methacrylate based polymers, acrylic polymer, ethylene-vinyl acetate base polymer, alpha-olefin-copolymer-maleic anhydride or vinylformic acid high alcohol ester multipolymer; Biofuel such as the plam oil biofuel high to saturated fatty acid content, methacrylate based polymers, acrylic polymer and the composite result of use of ethylene-vinyl acetate base polymer are better than independent use in the above-mentioned cold flow improver; Biofuel such as rapeseed oil biofuel, the soybean oil biofuel etc. lower to saturated fatty acid content, the independent result of use of above-mentioned cold flow improver is better.
The preparation method of technique scheme modifying agent is: take by weighing 1～10 part of antioxidant, 0～5 part of antioxidant synergistic agent by weight, join among 50～100 parts of RME, be heated to 40 ℃ under the condition of stirring, antioxidant is dissolved fully, add 5～50 parts of cold flow improvers then, stirring and evenly mixing is mixed with modifying agent; In this modifying agent, antioxidant concentration is 1～10% by weight, and synergistic agent concentration is 0～5%, and cold flow improver concentration is 5～50%.
Another technical scheme of the present invention is:
Form by antioxidant, anti-oxidant synergistic agent, dehydrated alcohol, RME and cold flow improver mixed preparing, each component concentration is by weight: 1～5 part of antioxidant, 0～5 part of anti-oxidant synergistic agent, 5～50 parts of dehydrated alcohols, RME40～90 part, 5～50 parts of cold flow improvers.
Described antioxidant is fat-soluble not strong antioxidant, mainly comprises Tenox PG (PG), can also comprise tea-polyphenol, sesamol, Rosmarinus officinalis bis-phenol, oxymethoxyallylbenzene or Vanillin.
Described anti-oxidant synergistic agent is L-Quicifal (AP) or phytic acid.
Above-mentioned fat-soluble not strong antioxidant and VE or be better than single use with the composite result of use of VE, AP.
Described cold flow improver is methacrylate based polymers, acrylic polymer, ethylene-vinyl acetate base polymer, alpha-olefin-copolymer-maleic anhydride or vinylformic acid high alcohol ester multipolymer, biofuel such as the plam oil biofuel high to saturated fatty acid content, methacrylate based polymers, acrylic polymer and the composite result of use of ethylene-vinyl acetate base polymer are better than independent use in the above-mentioned cold flow improver; Biofuel such as rapeseed oil biofuel, the soybean oil biofuel etc. lower to saturated fatty acid content, the independent result of use of above-mentioned cold flow improver is better.
The preparation method of technique scheme modifying agent is: take by weighing 1～5 part of antioxidant, 0～5 part of antioxidant synergistic agent by weight, join in 5～50 parts of dehydrated alcohols, stirring is dissolved it fully, add 40～90 parts of RME again, add 5～50 parts of cold flow improvers behind the mixing, stirring and evenly mixing is mixed with modifying agent; In this modifying agent, antioxidant concentration 1～5% by weight, synergistic agent concentration 0～5%, cold flow improver concentration 5～50%.
RME and dehydrated alcohol do not have the improvement effect as solvent to oxidation stability of biodiesel and low-temperature fluidity in the above-mentioned biological diesel modifying agent.
The use addition means of biological diesel modifying agent of the present invention in biofuel is: under stirring condition, take by weighing 1～5 part of biological diesel modifying agent by weight, join in 100 parts of biofuel, stir 10～50min, until modifying agent complete dispersing and dissolving in biofuel, make in the biofuel solution, antioxidant concentration reaches 0.005%～2% (w/w) by weight, synergistic agent concentration reaches 0～1% (w/w), and cold flow improver concentration reaches 0.1%～5% (w/w).
The preferred rapeseed oil of indication biofuel of the present invention, discarded food oils, soybean oil, plam oil are the stable fatty acid methyl ester admixture of every quality index that raw material makes.
The invention has the beneficial effects as follows:
1) can improve oxidation stability of biodiesel, under the situation of comparatively economic addition, but the oxidation induction period of significant prolongation biofuel under 110 ℃ of conditions, oxidation induction period prolongs 5～100h than original sample; Simultaneously several low temperature flow improver for diesel fuel are studied, its composite use can improve effect to the high biodiesel lower-temperature fluidity of saturated fatty acid methyl ester content and significantly be better than single diesel pour inhibitor, can make the biofuel cold filter clogging temperature reduce by 2～15 ℃.The mixture oxidation stability conformance with standard requirement that modifying agent of the present invention and biofuel are formed can store for a long time, and is fit to use at low temperatures.
2) the present invention is directed to different material source biofuel characteristics, optimized antioxidant, antioxidant synergistic agent, cold flow improver and the prescription thereof of suitable different biofuel, the series of biologic diesel oil modifying agent of developing has adaptability widely to multiple biofuel.
3) the present invention carries out antioxidant, synergistic agent and cold flow improver preferably composite, and at different antioxidant characteristics, study the compound method of simple and easy economy, it is mixed with convenient liquid stoste of adding, make the interpolation process have stronger operability, use very conveniently, it is low to add cost simultaneously, to improving biodiesel quality, the acceleration biofuel is promoted the use of has stronger practicality and economy.
4) solvent of the present invention mainly adopts RME, and the oxidation stability of himself is stronger, can carry out the storage of long period, and low-temperature fluidity is better simultaneously, can use at a lower temperature.
Embodiment
The following examples have been described enforcement of the present invention.
The biological diesel modifying agent of Different Weight is added in the biofuel sample, make its dissolving mixing, carry out the test of Rancimat and cold filter clogging temperature then.
The ultimate principle and the basic operational steps of Rancimat test:
The measuring principle of Rancimat method is based on that bubbling air makes sample generation oxidation under the hot conditions, materials such as the volatile small molecule aldehyde that oxidation produces, ketone, acid import and fill distilled water in vitro, the changing conditions of record distilled water specific conductivity, the terminal point of oxidation-stabilized process shows the precipitous rising of specific conductivity, calculate the maximum value of specific conductivity, be the sample oxidation initial stage the time changing curve second derivative---the numerical value of inductive phase.Take by weighing about 3g biofuel sample (comprising blank sample and the sample that has added modifying agent), insert sample hose, under 110 ℃ of conditions, feed the air of 10L/h cleaning, the working sample oxidation induction period.Rancimat test of the present invention is carried out according to " Fat and Oil derivatives-Fatty Acid Methyl Esters (FAME)-Determinationof oxidation stability (accelerated oxidation test) " (EN 14112:2003), adopts Switzerland Wan Tong company 743 Oxidation of Fat and Oils to stablize the determinator test.
Cold filter clogging temperature definition and test operating procedure:
The biofuel cold filter clogging temperature refers to that sample cools off under prescribed condition, cross the top temperature of the time of strainer when being not more than 60s or sample and can not flowing back to test glass fully when sample can not flow through strainer or 20mL sample stream.Place hot water bath to be heated to 30 ± 5 ℃ the test glass that fills the 45mL sample, place then in the sleeve pipe that is cooled to the preset temperature cryostat in advance, when sample is cooled to than high 5～6 ℃ of cold filter clogging temperature of expection, beginning is measured for the first time, 1 ℃ of every reduction, repetitive operation is once passed through the not enough 20mL of sample of strainer up to 1min.
Embodiment 1-12: component concentration all by weight among the following embodiment.
Embodiment 1:
Modifying agent comprises following component: TBHQ, JN-2000 pour point depressant (Perfect's product).The preparation method is as follows: take by weighing 6gTBHQ by weight, add 100g quality RME preferably, be heated to 40 ℃ under the condition of stirring, TBHQ is dissolved fully, add the 10gJN-2000 pour point depressant then, stirring and evenly mixing is mixed with modifying agent.TBHQ content is 5.17% in this modifying agent, and JN-2000 pour point depressant content is 8.62%.It is as follows to add application process: take by weighing modifying agent 0.58g, add 50gRME, stirring and evenly mixing makes that TBHQ content is 0.06% in this RME sample, and JN-2000 pour point depressant content is 0.1%, and sample IP value and CFPP pH-value determination pH the results are shown in Table 1.
Embodiment 2:
Modifying agent comprises following component: TBHQ, VE, T818 pour point depressant (Shanghai Ren Yinglian economic trade development company limited product).The preparation method is as follows: take by weighing 2gTBHQ, 2gVE by weight, add 100g quality RME preferably, be heated to 40 ℃ under the condition of stirring, TBHQ, VE are dissolved fully, add the 10gT818 pour point depressant then, stirring and evenly mixing is mixed with modifying agent.TBHQ, VE content are respectively 1.75% in this modifying agent, and T818 pour point depressant content is 8.77%.It is as follows to add application process: take by weighing the 0.57g modifying agent, add 50gRME, stirring and evenly mixing makes that TBHQ, VE content are respectively 0.02% in this RME sample, and T818 pour point depressant content is 0.1%, and sample IP value and CFPP pH-value determination pH the results are shown in Table 1.
Embodiment 3:
Modifying agent comprises following component: PG, T818 pour point depressant, PRI-Flow pour point depressant (Beijing must promise letter environmental science and technology company limited produce).Compound method is as follows: take by weighing 2gPG, add the 10g dehydrated alcohol, stirring is dissolved it fully, adds 90g quality RME preferably again, adds 5gT818 pour point depressant and PRI-Flow pour point depressant behind the stirring and evenly mixing respectively, and stirring and evenly mixing is mixed with modifying agent.In this modifying agent, PG content is 1.79%, and T818 pour point depressant, PRI-Flow pour point depressant content are respectively 4.46%.It is as follows to add application process: take by weighing the 0.56g modifying agent, add 50gRME, stirring and evenly mixing makes that PG content is 0.02% in this RME sample, and T818 pour point depressant and PRI-Flow pour point depressant content are respectively 0.05%, and sample IP value and CFPP pH-value determination pH the results are shown in Table 1.
Embodiment 4:
Modifying agent comprises following component: BHT, BHA, AP, PRI-Flow pour point depressant.Compound method is as follows: take by weighing 2gAP, add the 50g dehydrated alcohol, stirring makes it dissolve back adding 50g quality RME preferably fully, stirring and evenly mixing, and then take by weighing 4gBHT, BHA respectively and add, stirring is dissolved it fully, adds the 10gPRI-Flow pour point depressant at last, and stirring and evenly mixing is mixed with modifying agent.In this modifying agent, the content of BHT, BHA is respectively 3.33%, and AP content is 1.67%, and PRI-Flow pour point depressant content is 8.34%.It is as follows to add application process: take by weighing the 0.6g modifying agent, add 50gRME, stirring and evenly mixing, make the content of BHT, BHA in this RME sample be respectively 0.04%, AP content is 0.02%, and the content of PRI-Flow pour point depressant is 0.1%, and sample IP value and CFPP pH-value determination pH the results are shown in Table 1.
Embodiment 5:
Modifying agent comprises following component: TBHQ, T818 pour point depressant.Compound method is as follows: take by weighing 2gTBHQ, add 100g quality RME preferably, be heated to 40 ℃ under the condition of stirring, it is dissolved fully, add the 10gT818 pour point depressant then, stirring and evenly mixing is mixed with modifying agent.In this modifying agent, TBHQ content is 1.79%, and T818 pour point depressant content is 8.93%.It is as follows to add application process: take by weighing the 0.56g modifying agent, add 50gPME, stirring and evenly mixing makes that TBHQ content is 0.02% in this PME sample, and T818 pour point depressant content is 0.1%, and sample IP value and CFPP pH-value determination pH the results are shown in Table 2.
Embodiment 6:
Modifying agent comprises following component: PG, JN-2000 pour point depressant (Perfect's product), ice spirit tablet pour point depressant (Taiyuan is iced clever diesel pour inhibitor company limited and produced).Compound method is as follows: take by weighing 2gPG, add the 10g dehydrated alcohol, stirring is dissolved it fully, adds 90g quality RME preferably again, adds 80gJN-2000 pour point depressant, 20g ice spirit tablet pour point depressant behind the stirring and evenly mixing, and stirring and evenly mixing is mixed with modifying agent.PG content is 0.99% in this modifying agent, and JN-2000 pour point depressant content is 39.60%, and ice spirit tablet pour point depressant content is 9.90%.It is as follows to add application process: take by weighing the 1.01g modifying agent, add 50gPME, stirring and evenly mixing, make that PG content is 0.02% in this PME sample, JN-2000 pour point depressant content is 0.8%, and ice spirit tablet pour point depressant content is 0.2%, and sample IP value and CFPP pH-value determination pH the results are shown in Table 2.
Embodiment 7:
Modifying agent comprises following component: PG, PRI-Flow pour point depressant, ice spirit tablet pour point depressant.Compound method is as follows: take by weighing 2gPG, add the 10g dehydrated alcohol, stirring is dissolved it fully, adds 90g quality RME preferably again, adds 40gPRI-Flow pour point depressant, 60g ice spirit tablet pour point depressant behind the stirring and evenly mixing respectively, and stirring and evenly mixing is mixed with modifying agent.In this modifying agent, PG content is 0.99%, and PRI-Flow pour point depressant, ice spirit tablet pour point depressant content are respectively 19.80%, 29.70%.It is as follows to add application process: take by weighing the 1.01g modifying agent, add 50gPME, stirring and evenly mixing, make that PG content is 0.02% in this PME sample, PRI-Flow pour point depressant content is 0.4%, and ice spirit tablet pour point depressant content is 0.6%, and sample IP value and CFPP pH-value determination pH the results are shown in Table 2.
Embodiment 8:
Modifying agent comprises following component: TBHQ, JN-2000 pour point depressant (Perfect's product).The preparation method is as follows: take by weighing 2gTBHQ by weight, add 100g quality RME preferably, be heated to 40 ℃ under the condition of stirring, TBHQ is dissolved fully, add the 30gJN-2000 pour point depressant then, stirring and evenly mixing is mixed with modifying agent.TBHQ content is 1.52% in this modifying agent, and JN-2000 pour point depressant content is 22.73%.It is as follows to add application process: take by weighing modifying agent 0.66g, add 50gSME, stirring and evenly mixing makes that TBHQ content is 0.02% in this SME sample, and JN-2000 pour point depressant content is 0.3%, and sample IP value and CFPP pH-value determination pH the results are shown in Table 3.
Embodiment 9:
Modifying agent comprises following component: TBHQ, PRI-Flow pour point depressant, TC type pour point depressant (the prosperous brave petrochemical industry additive of Shandong Zibo factory produces).The preparation method is as follows: take by weighing 2gTBHQ by weight, add 100g quality RME preferably, be heated to 40 ℃ under the condition of stirring, TBHQ is dissolved fully, add 8g PRI-Flow pour point depressant, 2g TC type pour point depressant then, stirring and evenly mixing is mixed with modifying agent.TBHQ content is 1.79% in this modifying agent, and PRI-Flow pour point depressant content is 7.14%, and TC type pour point depressant content is 1.79%.It is as follows to add application process: take by weighing modifying agent 0.59g, add 50gSME, stirring and evenly mixing, make that TBHQ content is 0.02% in this SME sample, PRI-Flow pour point depressant content is 0.08%, and TC type pour point depressant content is 0.02%, and sample IP value and CFPP pH-value determination pH the results are shown in Table 3.
Embodiment 10:
Modifying agent comprises following component: BHT, PRI-Flow pour point depressant.Compound method is as follows: take by weighing 8gBHT, add 100g quality RME preferably, stirring is dissolved it fully, adds 50g PRI-Flow pour point depressant then, and stirring is mixed with modifying agent.In this modifying agent, BHT content is 5.06%, and PRI-Flow pour point depressant content is 31.65%.It is as follows to add application process: take by weighing the 0.79g modifying agent, add 50gSME, stirring and evenly mixing makes that BHT content is 0.08% in this SME sample, and PRI-Flow pour point depressant content is 0.5%, and sample IP value and CFPP pH-value determination pH the results are shown in Table 3.
Embodiment 11:
Modifying agent comprises following component: PG, T818 pour point depressant, PRI-Flow pour point depressant.Compound method is as follows: take by weighing 4gPG, add the 10g dehydrated alcohol, stirring is dissolved it fully, adds 90g quality RME preferably again, adds 40gT818 pour point depressant, 10gPRI-Flow pour point depressant behind the stirring and evenly mixing, and stirring and evenly mixing is mixed with modifying agent.In this modifying agent, PG content is 2.60%, and T818 pour point depressant, PRI-Flow pour point depressant content are respectively 25.32%, 6.33%.It is as follows to add application process: take by weighing the 0.77g modifying agent, add 50gWME, stirring and evenly mixing makes that PG content is 0.04% in this WME sample, T818 pour point depressant, PRI-Flow pour point depressant content are respectively 0.4%, 0.1%, and sample IP value and CFPP pH-value determination pH the results are shown in Table 4.
Embodiment 12:
Modifying agent comprises following component: TBHQ, PRI-Flow pour point depressant, ice spirit tablet pour point depressant.Compound method is as follows: take by weighing 6gTBHQ, add 100g quality RME preferably, add 40gPRI-Flow pour point depressant, 60g ice spirit tablet pour point depressant behind the stirring and evenly mixing respectively, stirring and evenly mixing is mixed with modifying agent.In this modifying agent, PG content is 2.91%, and PRI-Flow pour point depressant, ice spirit tablet pour point depressant content are respectively 19.42%, 29.13%.It is as follows to add application process: take by weighing the 1.03g modifying agent, add 50gWME, stirring and evenly mixing, make that TBHQ content is 0.06% in this WME sample, PRI-Flow pour point depressant content is 0.4%, and ice spirit tablet pour point depressant content is 0.6%, and sample IP value and CFPP pH-value determination pH the results are shown in Table 4.
Table 1 has been listed the test result of the modifying agent of embodiment 1-4 to rapeseed oil biofuel (RME) effect.
The effect of table 1 biological diesel modifying agent in RME
| Modifying agent | Antioxidant+synergistic agent concentration, % (w/w) | Cold flow improver concentration, % (w/w) | Oxidation induction period, h | Cold filter clogging temperature, ℃ |
| Embodiment 1 | 0.06 | 0.1 | 18.72 | -24 |
| Embodiment 2 | 0.04 | 0.1 | 11.57 | -23 |
| Embodiment 3 | 0.02 | 0.1 | 17.86 | -19 |
| Embodiment 4 | 0.1 | 0.1 | 25.54 | -22 |
Annotate: RME check sample IP is 5.93h, and CFPP is-11 ℃.
Table 2 has been listed the test result of the modifying agent of embodiment 5-7 to plam oil biofuel (PME) effect.
The effect of table 2 biological diesel modifying agent in PME
| Modifying agent | Antioxidant+synergistic agent concentration, % (w/w) | Cold flow improver concentration, % (w/w) | Oxidation induction period, h | Cold filter clogging temperature, ℃ |
| Embodiment 5 | 0.02 | 0.1 | 36.52 | 3 |
| Embodiment 6 | 0.02 | 1.0 | 43.65 | 0 |
| Embodiment 7 | 0.02 | 1.0 | 42.32 | 0 |
Annotate: PME check sample IP is 21.42h, and CFPP is 8 ℃.
Table 3 has been listed the test result of the modifying agent of embodiment 8-10 to soybean oil biofuel (SME) effect.
The effect of table 3 biological diesel modifying agent in SME
| Modifying agent | Antioxidant+synergistic agent concentration, % (w/w) | Cold flow improver concentration, % (w/w) | Oxidation induction period, h | Cold filter clogging temperature, ℃ |
| Embodiment 8 | 0.02 | 0.3 | 19.69 | -10 |
| Embodiment 9 | 0.02 | 0.1 | 18.62 | -11 |
| Embodiment 10 | 0.08 | 0.5 | 131 | -13 |
Annotate: SME check sample IP is 0.31h, and CFPP is-6 ℃.
Table 4 has been listed the test result of the modifying agent of embodiment 11,12 to waste grease biofuel (WME) effect.
The effect of table 4 biological diesel modifying agent in WME
| Modifying agent | Antioxidant+synergistic agent concentration, % (w/w) | Low-temperature performance modifying agent concentration, % (w/w) | Oxidation induction period, h | Cold filter clogging temperature, ℃ |
| Embodiment 11 | 0.04 | 0.5 | 9.39 | -4 |
| Embodiment 12 | 0.06 | 1.0 | 16.67 | -5 |
Annotate: WME check sample IP is 0.18h, and CFPP is 2 ℃.
Claims (10)
1, a kind of biological diesel modifying agent, it is characterized in that being formed by antioxidant, anti-oxidant synergistic agent, rapeseed oil biofuel and cold flow improver mixed preparing, each component concentration is by weight: 1～10 part of antioxidant, 0～5 part of anti-oxidant synergistic agent, 50～100 parts of rapeseed oil biofuel, 5～50 parts of cold flow improvers.
2, biological diesel modifying agent according to claim 1, it is characterized in that described antioxidant is fat-soluble strong antioxidant, comprise tertiarybutylhydroquinone, 3,5-di-t-butyl-4-hydroxytoluene, 3-tertiary butyl-4-hydroxy-phenylmethylether or vitamin-E, also comprise 3,5-di-t-butyl-4-hydroxyl-phenylmethylether, dihydroguaiaretic acid, guaiac(um), 2 fall, 4,5-trihydroxy--propylbenzene ketone, 4-methylol-2,6-DI-tert-butylphenol compounds or 6-oxyethyl group-1,2-dihydro-2,2,4-trimethylammonium Kui quinoline.
3, biological diesel modifying agent according to claim 1 is characterized in that described antioxidant by 3-tertiary butyl-4-hydroxy-phenylmethylether and 3, and 5-di-t-butyl-4-hydroxytoluene is used in combination.
4,, it is characterized in that described anti-oxidant synergistic agent is L-Quicifal or phytic acid, phosphatide, citric acid, tartrate according to claim 2 or 3 described biological diesel modifying agents.
5, biological diesel modifying agent according to claim 1 and 2 is characterized in that described cold flow improver is methacrylate based polymers, acrylic polymer, ethylene-vinyl acetate base polymer, alpha-olefin-copolymer-maleic anhydride or vinylformic acid high alcohol ester multipolymer.
6, biological diesel modifying agent according to claim 1 and 2 is characterized in that described cold flow improver is by methacrylate based polymers, acrylic polymer and composite the forming of ethylene-vinyl acetate base polymer combination.
7, the preparation method of biological diesel modifying agent according to claim 1, it is characterized in that taking by weighing by weight 1～10 part of antioxidant, 0～5 part of antioxidant synergistic agent, join in 50～100 parts of rapeseed oil biofuel, be heated to 40 ℃ under the condition of stirring, antioxidant is dissolved fully, add 5～50 parts of cold flow improvers then, stirring and evenly mixing is mixed with modifying agent; In this modifying agent, antioxidant concentration is 1～10% by weight, and synergistic agent concentration is 0～5%, and cold flow improver concentration is 5～50%.
8, a kind of biological diesel modifying agent, it is characterized in that forming by antioxidant, anti-oxidant synergistic agent, dehydrated alcohol, RME and cold flow improver mixed preparing, each component concentration is by weight: 1～5 part of antioxidant, 0～5 part of anti-oxidant synergistic agent, 5～50 parts of dehydrated alcohols, 40～90 parts of rapeseed oil biofuel, 5～50 parts of cold flow improvers.
9, biological diesel modifying agent according to Claim 8 is characterized in that described antioxidant is fat-soluble not strong antioxidant, comprises Tenox PG (PG), also comprises tea-polyphenol, sesamol, Rosmarinus officinalis bis-phenol, oxymethoxyallylbenzene or Vanillin.
10, the preparation method of biological diesel modifying agent according to claim 7, it is characterized in that taking by weighing by weight 1～5 part of antioxidant, 0～5 part of antioxidant synergistic agent, join in 5～50 parts of dehydrated alcohols, stirring is dissolved it fully, add 40～90 parts of rapeseed oil biofuel again, add 5～50 parts of cold flow improvers behind the mixing, stirring and evenly mixing is mixed with modifying agent; In this modifying agent, antioxidant concentration 1～5% by weight, synergistic agent concentration 0～5%, cold flow improver concentration 5～50%.
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