CN101418226A - Method for preparing biodiesel by using N-heterocyclic carbine carbondioxide adducts as catalyst - Google Patents
Method for preparing biodiesel by using N-heterocyclic carbine carbondioxide adducts as catalyst Download PDFInfo
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- CN101418226A CN101418226A CNA2008102355934A CN200810235593A CN101418226A CN 101418226 A CN101418226 A CN 101418226A CN A2008102355934 A CNA2008102355934 A CN A2008102355934A CN 200810235593 A CN200810235593 A CN 200810235593A CN 101418226 A CN101418226 A CN 101418226A
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- 239000003225 biodiesel Substances 0.000 title claims abstract description 30
- 239000003054 catalyst Substances 0.000 title claims abstract description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical class O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims description 27
- 238000000034 method Methods 0.000 title abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 15
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 5
- 239000003921 oil Substances 0.000 claims description 55
- 235000019198 oils Nutrition 0.000 claims description 55
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- 229910052799 carbon Inorganic materials 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 22
- -1 Oleum Gossypii semen Substances 0.000 claims description 14
- 239000002551 biofuel Substances 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 235000013311 vegetables Nutrition 0.000 claims description 11
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 10
- 125000005843 halogen group Chemical group 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 239000003549 soybean oil Substances 0.000 claims description 10
- 235000012424 soybean oil Nutrition 0.000 claims description 10
- 150000001721 carbon Chemical group 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 235000019483 Peanut oil Nutrition 0.000 claims description 4
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 239000000312 peanut oil Substances 0.000 claims description 4
- 239000002383 tung oil Substances 0.000 claims description 4
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 claims description 3
- 235000002991 Coptis groenlandica Nutrition 0.000 claims description 2
- 244000247747 Coptis groenlandica Species 0.000 claims description 2
- 241001048891 Jatropha curcas Species 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 235000009508 confectionery Nutrition 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 210000000582 semen Anatomy 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000008159 sesame oil Substances 0.000 claims description 2
- 235000011803 sesame oil Nutrition 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 4
- 229910021645 metal ion Inorganic materials 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000012075 bio-oil Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000008158 vegetable oil Substances 0.000 abstract 3
- 125000004185 ester group Chemical group 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000036632 reaction speed Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 40
- 235000014113 dietary fatty acids Nutrition 0.000 description 22
- 239000000194 fatty acid Substances 0.000 description 22
- 229930195729 fatty acid Natural products 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 20
- 238000004458 analytical method Methods 0.000 description 10
- 150000004665 fatty acids Chemical class 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 230000009466 transformation Effects 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 102000004190 Enzymes Human genes 0.000 description 6
- 108090000790 Enzymes Proteins 0.000 description 6
- 150000004702 methyl esters Chemical class 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 238000005815 base catalysis Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 3
- 244000068988 Glycine max Species 0.000 description 3
- 235000010469 Glycine max Nutrition 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007171 acid catalysis Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000593 microemulsion method Methods 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 235000020238 sunflower seed Nutrition 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000010773 plant oil Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Landscapes
- Liquid Carbonaceous Fuels (AREA)
- Fats And Perfumes (AREA)
Abstract
The invention discloses a method for producing biodiesel in the presence of a catalyst of an N-heterocyclic carbene-carbon dioxide adduct and belongs to the technical field of bio-oil synthesis and green renewable energy resources. The method is to produce biodiesel by ester exchange reaction of lower alcohols and vegetable oil at 55 to 120 DEG C in the presence of a catalyst of an N-heterocyclic carbene-carbon dioxide adduct, wherein the molar ratio of the vegetable oil to the lower alcohols is between 1 to 6 and 1 to 30, the mass of the catalyst is 0.1 to 5 percent of the mass of the vegetable oil and the ester exchange reaction is carried out for 2 to 100 minutes. The method has the advantages of good catalyst controllability, high reaction activity, high reaction speed, mild reaction conditions, no introduction of metal ions, no equipment corrosion and simple post treatment of products.
Description
Technical field
The invention belongs to synthetic, the technical field of green regenerative energy sources of bio-oil materials, particularly a kind of method of N-heterocycle carbine carbon dioxide adduct catalysis for preparing biodiesel oil.
Background technology
Along with the mankind growing to energy demand, fossil energy constantly reduces.Uneven consumer goods prices and the environment given of energy supply and demand all caused very big pressure, develops the alternative energy and becomes inexorable trend.Renewable energy source as cleaning---biofuel becomes the focus of people's research gradually.
Biofuel is the mixture of lipid acid short-chain alkyl ester, wherein the triglyceride level of lipid acid multi-source in vegetables oil.The main preparation methods of biofuel has: hybrid system, micro emulsion method, pyrolysis method, ester-interchange method etc.
Hybrid system and micro emulsion method all belong to physical method, the biofuel viscosity of production greatly, not volatile, can cause problems such as the coking of engine nozzle, piston ring are stuck, carbon laydown.Pyrolysis method at high temperature carries out, and needs to add catalyzer, and reaction is difficult to control, conversion unit costliness.
Ester exchange method is converted to fatty acid ester with full-bodied animal-plant oil and low-carbon alcohol generation transesterification reaction, is the most frequently used biodiesel oil preparing process, and it comprises approach such as acid catalysis, base catalysis, enzyme catalysis.
The enzyme that enzymatic process relates to, price are generally all very expensive.Xu Yan etc. (CN101205474) disclose the full cellular fat enzyme catalysis of the low-cost magnificent root enzyme of a kind of employing and have prepared method of bio-diesel oil, effectively reduced the enzyme catalysis cost, still, because enzyme easy inactivation in low-carbon alcohol, alcohol must be added in batches, and need 48～72 hours reaction times.
There is the problem of long reaction time equally in acid catalysis, and the sulfuric acid of Chang Zuowei catalyzer etc. is strong to the corrodibility of equipment.Yang Jianguo etc. (CN101250422) disclose a kind of biodiesel oil preparing process of solid acid catalysis, have reduced the corrosion of reaction process to equipment, and will shorten in the reaction times about 8 hours, but the still inevitable alkaline cleaning procedure of this method.
Traditional base catalysis is a catalyzer with sodium hydroxide, potassium hydroxide, sodium methoxide etc. generally.The methyl alcohol and the triglyceride level that are most commonly used to prepare biofuel do not dissolve each other, between the substrate rate of mass transfer low be the reason that directly influences speed of reaction.(V.Mao, S.K.Konar and D.G..B.Boocock, J.Am.Oil chem.Soc., 2004,81,803-808 such as Dived; US6712867) select for use tetrahydrofuran (THF) as solubility promoter, studied a kind of single-phase base catalysis and prepared method of bio-diesel oil, effectively improved the efficient that base catalysis prepares biofuel.But, under the lower situation of alcohol/oil ratio, along with the carrying out of reaction, glycerine is separated out, and reaction system no longer is single-phase, because above-mentioned alkaline catalysts more is soluble in the big glycerine phase of polarity, make that catalyst content reduces rapidly in the substrate, thereby cause speed of reaction to descend rapidly.
Cabbeen is the efficient organic catalyst of a class, enjoys chemist's concern in recent years.Two research groups of Nolan and Hedrick (G.A.Grasa, R.M.Kissling and S.P.Nolan, Org.Lett., 2002,4,3583-3586; G.W.Nyce, J.A.Lamboy and J.L.Hedrick, Org.Lett., 2002,4,3587-3590) almost reported the reaction of N-heterocycle carbine catalytic transesterification simultaneously, the preparation that is used for catalysis biological diesel oil for Cabbeen is laid a good foundation.Recently, it is substrate with the vegetable and animals oils that GAO (WO2008/070756) discloses a kind of, the method for preparing fatty acid alkyl ester, process comprising Cabbeen alcohol adducts catalysis transesterify, some the Cabbeen alcohol adducts that relates to must heat under vacuum condition just can discharge active Cabbeen, has increased operation easier.N-heterocycle carbine carbon dioxide adduct is stable to empty G﹠W, again can by change temperature, solvent controlled discharge active Cabbeen, as catalyzer, storage and application are all very convenient, because containing metal not in its molecule is difficult for introducing the metal ion that influences biodiesel quality in product.Thereby, in the preparation of biofuel, have good application prospects.
Summary of the invention
The objective of the invention is to propose a kind of method of N-heterocycle carbine carbon dioxide adduct catalysis for preparing biodiesel oil, have good catalyst controllability, the reactive behavior height, speed of response is fast, and reaction conditions is gentle relatively, does not introduce metal ion, no equipment corrosion, advantage such as product postprocessing is simple.
The present invention proposes a kind of preparation method of bio-diesel oil, it is characterized in that vegetables oil and low-carbon alcohol are mixed, and adds N-heterocycle carbine carbon dioxide adduct as catalyzer, and mixing and stirring is reacted, and obtains the product biofuel after separating.
In above-mentioned preparation method of bio-diesel oil, the structural formula of described N-heterocycle carbine carbon dioxide adduct is formula (I), formula (II), formula (III) or formula (IV)
In the structural formula of above-mentioned N-heterocycle carbine carbon dioxide adduct, R in the structural formula of described N-heterocycle carbine carbon dioxide adduct
1, R
2Be selected from hydrogen, alkyl with 1～10 carbon atom, has 1～10 carbon atom and by the alkyl of one or more replacements in halogen atom, hydroxyl, phenyl and the cyano group, cycloalkyl with 3～6 carbon atoms, phenyl or by the identical or different group in the phenyl of one or more replacements in halogen atom, hydroxyl, alkyl and the cyano group; R
3, R
4Be selected from hydrogen, halogen atom, cyano group, hydroxyl, alkyl with 1～4 carbon atom, has 1～4 carbon atom and by the alkyl of one or more replacements in halogen atom, hydroxyl, phenyl and the cyano group, phenyl or by the identical or different group in the phenyl of one or more replacements in halogen atom, hydroxyl, alkyl and the cyano group.
In above-mentioned preparation method of bio-diesel oil, described vegetables oil is soybean oil, Trisun Oil R 80, sweet oil, rapeseed oil, peanut oil, sesame oil, plam oil, Viscotrol C, Oleum Gossypii semen, tung oil, coptis wood oil, jatropha curcas seed oil or Ka Lanjia seeds of trees oil.
In above-mentioned preparation method of bio-diesel oil, described low-carbon alcohol is methyl alcohol, ethanol, n-propyl alcohol, Virahol or propyl carbinol.
In above-mentioned preparation method of bio-diesel oil, when being methyl alcohol or ethanol, low-carbon alcohol in pure oil mixt, adds solubility promoter.
In above-mentioned preparation method of bio-diesel oil, described solubility promoter is a tetrahydrofuran (THF), 1,4-dioxane, ether, diisopropyl ether or t-butyl methyl ether; The mol ratio of vegetables oil and solubility promoter is 1:7～4:1.
In above-mentioned preparation method of bio-diesel oil, the mol ratio of described vegetables oil and low-carbon alcohol is 1:6～1:30, and catalyst levels is 0.1～5% of a vegetables oil quality.
In above-mentioned preparation method of bio-diesel oil, described temperature of reaction is 55～120 ℃, 2～100 minutes reaction times.
In above-mentioned preparation method of bio-diesel oil, described separation method is that reaction solution is washed, standing demix, isolate upper strata ester phase, obtain product biofuel or distillation and remove the mixed solution of unreacted low-carbon alcohol or unreacted low-carbon alcohol and solubility promoter, standing demix is isolated upper strata ester phase, obtains product biofuel profitable fruit of the present invention:
The distinguishing feature of method of the present invention is to select for use N-heterocycle carbine carbon dioxide adduct to make catalyzer.Selectivity adds solubility promoter, and reaction system is carried out under single-phase condition all the time.Speed of response is fast, and reaction conditions is gentle relatively, does not introduce metal ion, no equipment corrosion, and product postprocessing is simple.
Embodiment:
According to following embodiment, the present invention may be better understood.Yet, those skilled in the art will readily understand that the described concrete material proportion of embodiment, processing condition and result only are used to illustrate the present invention, and should also can not limit the present invention described in detail in claims.
The N-heterocycle carbine carbon dioxide adduct numbering and the structure that relate among table 1 embodiment
Below the catalyzer counter structure of each embodiment see Table 1.
Embodiment 1
65 ℃ of temperature of reaction; under the nitrogen protection,, add catalyst A (catalyzer be soybean oil quality 0.1%) with the uniform mixing (mol ratio is 1:6:7) of soybean oil, methyl alcohol, tetrahydrofuran (THF); stir; termination reaction after 2 minutes steams unreacted methanol and tetrahydrofuran (THF), standing demix; take out the upper strata product; utilize the analysis of Agilent GC-7890A gas chromatograph, recording the fatty acid triglycercide transformation efficiency is 90%, and the fatty acid ester content of middle methyl esters mutually is 92%.
Embodiment 2
55 ℃ of temperature of reaction, under the nitrogen protection, with tung oil, methyl alcohol, 1; the uniform mixing liquid of 4-dioxane (mol ratio is 1:10:4); add catalyst B (catalyzer be tung oil quality 0.5%), stir termination reaction after 10 minutes; after the warm water washing three times; standing demix takes out the upper strata product, utilizes the analysis of Agilent GC-7890A gas chromatograph; recording the fatty acid triglycercide transformation efficiency is 96%, and the fatty acid ester content of middle methyl esters mutually is 97%.
Embodiment 3
60 ℃ of temperature of reaction; under the nitrogen protection,, add catalyzer C (catalyzer be peanut oil quality 1%) with the uniform mixing liquid (mol ratio is 1:10:4) of peanut oil, methyl alcohol, tetrahydrofuran (THF); stir; termination reaction after 30 minutes steams unreacted methanol and tetrahydrofuran (THF), standing demix; take out the upper strata product; utilize the analysis of Agilent GC-7890A gas chromatograph, recording the fatty acid triglycercide transformation efficiency is 98%, and the fatty acid ester content of middle methyl esters mutually is 98%.
Embodiment 4
65 ℃ of temperature of reaction; under the nitrogen protection,, add catalyzer D (catalyzer be sunflower seed oil quality 3%) with the uniform mixing liquid (mol ratio is 2:40:1) of sunflower seed oil, methyl alcohol, diisopropyl ether; stir; termination reaction after 30 minutes steams unreacted methanol and diisopropyl ether, standing demix; take out the upper strata product; utilize the analysis of Agilent GC-7890A gas chromatograph, recording the fatty acid triglycercide transformation efficiency is 98%, and the fatty acid ester content of middle methyl esters mutually is 98%.
Embodiment 5
65 ℃ of temperature of reaction; under the nitrogen protection,, add catalyzer E (catalyzer be soya-bean oil quality 5%) with the uniform mixing liquid (mol ratio is 4:120:1) of soya-bean oil, methyl alcohol, tetrahydrofuran (THF); stir; termination reaction after 30 minutes steams unreacted methanol and tetrahydrofuran (THF), standing demix; take out the upper strata product; utilize the analysis of Agilent GC-7890A gas chromatograph, recording the fatty acid triglycercide transformation efficiency is 99%, and the fatty acid ester content of middle methyl esters mutually is 99%.
Embodiment 6
75 ℃ of temperature of reaction; under the nitrogen protection,, add catalyzer F (catalyzer be soybean oil quality 1%) with the uniform mixing liquid (mol ratio is 1:10:4) of soybean oil, ethanol, ether; stir; termination reaction after 30 minutes steams unreacted ethanol and ether, standing demix; take out the upper strata product; utilize the analysis of Agilent GC-7890A gas chromatograph, recording the fatty acid triglycercide transformation efficiency is 97%, and the fatty acid ester content of middle ethyl ester mutually is 97%.
Embodiment 7
80 ℃ of temperature of reaction; under the nitrogen protection,, add catalyzer G (catalyzer be soybean oil quality 1%) with the uniform mixing liquid (mol ratio is 1:20:5) of Viscotrol C, ethanol, tetrahydrofuran (THF); stir; termination reaction after 60 minutes steams unreacted ethanol and tetrahydrofuran (THF), standing demix; take out the upper strata product; utilize the analysis of Agilent GC-7890A gas chromatograph, recording the fatty acid triglycercide transformation efficiency is 96%, and the fatty acid ester content of middle ethyl ester mutually is 97%.
Embodiment 8
100 ℃ of temperature of reaction; under the nitrogen protection,, add catalyzer H (catalyzer be rapeseed oil quality 1%) with the uniform mixing liquid (mol ratio is 1:10) of rapeseed oil, propyl alcohol; stir; termination reaction after 60 minutes steams unreacted propyl alcohol, standing demix; take out the upper strata product; utilize the analysis of Agilent GC-7890A gas chromatograph, recording the fatty acid triglycercide transformation efficiency is 96%, and the fatty acid ester content of middle propyl ester mutually is 95%.
Embodiment 9
85 ℃ of temperature of reaction; under the nitrogen protection,, add catalyst I (catalyzer be soybean oil quality 1%) with the uniform mixing liquid (mol ratio is 1:10) of soybean oil, Virahol; stir; termination reaction after 60 minutes steams unreacted Virahol, standing demix; take out the upper strata product; utilize the analysis of Agilent GC-7890A gas chromatograph, recording the fatty acid triglycercide transformation efficiency is 95%, and the fatty acid ester content of middle isopropyl ester mutually is 96%.
Embodiment 10
120 ℃ of temperature of reaction; under the nitrogen protection,, add catalyzer J (catalyzer be soybean oil quality 1%) with the uniform mixing liquid (mol ratio is 1:10) of soya-bean oil, butanols; stir; termination reaction after 100 minutes steams unreacted butanols, standing demix; take out the upper strata product; utilize the analysis of Agilent GC-7890A gas chromatograph, recording the fatty acid triglycercide transformation efficiency is 95%, and the fatty acid ester content of middle butyl ester mutually is 93%.
Claims (10)
1, a kind of preparation method of bio-diesel oil is characterized in that vegetables oil and low-carbon alcohol are mixed, and adds N-heterocycle carbine carbon dioxide adduct as catalyzer, and mixing and stirring is reacted, and obtains the product biofuel after separating.
2, a kind of preparation method of bio-diesel oil according to claim 1, the structural formula that it is characterized in that described N-heterocycle carbine carbon dioxide adduct are formula (I), formula (II), formula (III) or formula (IV)
3, a kind of preparation method of bio-diesel oil according to claim 2 is characterized in that R in the structural formula of described N-heterocycle carbine carbon dioxide adduct
1, R
2Be selected from hydrogen, alkyl with 1～10 carbon atom, has 1～10 carbon atom and by the alkyl of one or more replacements in halogen atom, hydroxyl, phenyl and the cyano group, cycloalkyl with 3～6 carbon atoms, phenyl or by the identical or different group in the phenyl of one or more replacements in halogen atom, hydroxyl, alkyl and the cyano group; R
3, R
4Be selected from hydrogen, halogen atom, cyano group, hydroxyl, alkyl with 1～4 carbon atom, has 1～4 carbon atom and by the alkyl of one or more replacements in halogen atom, hydroxyl, phenyl and the cyano group, phenyl or by the identical or different group in the phenyl of one or more replacements in halogen atom, hydroxyl, alkyl and the cyano group.
4, a kind of preparation method of bio-diesel oil according to claim 1 is characterized in that described vegetables oil is soybean oil, Trisun Oil R 80, sweet oil, rapeseed oil, peanut oil, sesame oil, plam oil, Viscotrol C, Oleum Gossypii semen, tung oil, coptis wood oil, jatropha curcas seed oil or Ka Lanjia seeds of trees oil.
5, a kind of preparation method of bio-diesel oil according to claim 1 is characterized in that described low-carbon alcohol is methyl alcohol, ethanol, n-propyl alcohol, Virahol or propyl carbinol.
6, a kind of preparation method of bio-diesel oil according to claim 1, the mol ratio that it is characterized in that described vegetables oil and low-carbon alcohol is 1:6～1:30.
7, a kind of preparation method of bio-diesel oil according to claim 1 is characterized in that described catalyst levels is 0.1～5% of a vegetables oil quality.
8, a kind of preparation method of bio-diesel oil according to claim 1 is characterized in that described temperature of reaction is 55～120 ℃.
9, a kind of preparation method of bio-diesel oil according to claim 1 is characterized in that, the described reaction times is 2～100 minutes.
10, a kind of preparation method of bio-diesel oil according to claim 1, it is characterized in that separation method is that reaction solution is washed, standing demix, isolate upper strata ester phase, obtain product biofuel or distillation and remove the mixed solution of unreacted low-carbon alcohol or unreacted low-carbon alcohol and solubility promoter, standing demix is isolated upper strata ester phase, obtains the product biofuel.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093164A (en) * | 2010-11-25 | 2011-06-15 | 中国科学院过程工程研究所 | Method for simultaneously preparing glycol and carbonate by catalysis |
| CN103160380A (en) * | 2013-03-28 | 2013-06-19 | 南京工业大学 | Method for preparing biodiesel by use of 1,2,3-triazole carbene carbon dioxide adduct catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100567458C (en) * | 2006-06-08 | 2009-12-09 | 河南农业大学 | A kind of method of utilizing lipase-catalyzed biodiesel synthesis |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093164A (en) * | 2010-11-25 | 2011-06-15 | 中国科学院过程工程研究所 | Method for simultaneously preparing glycol and carbonate by catalysis |
| CN102093164B (en) * | 2010-11-25 | 2013-06-05 | 中国科学院过程工程研究所 | Method for simultaneously preparing glycol and carbonate by catalysis |
| CN103160380A (en) * | 2013-03-28 | 2013-06-19 | 南京工业大学 | Method for preparing biodiesel by use of 1,2,3-triazole carbene carbon dioxide adduct catalyst |
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