CN101418226B - 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
- Publication number
- CN101418226B CN101418226B CN2008102355934A CN200810235593A CN101418226B CN 101418226 B CN101418226 B CN 101418226B CN 2008102355934 A CN2008102355934 A CN 2008102355934A CN 200810235593 A CN200810235593 A CN 200810235593A CN 101418226 B CN101418226 B CN 101418226B
- Authority
- CN
- China
- Prior art keywords
- oil
- bio
- preparation
- reaction
- carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003225 biodiesel Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 20
- 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
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 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 57
- 235000019198 oils Nutrition 0.000 claims description 57
- 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 21
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000002551 biofuel Substances 0.000 claims description 13
- 235000013311 vegetables Nutrition 0.000 claims description 13
- 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
- 125000005843 halogen group Chemical group 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 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
- -1 Oleum Gossypii semen Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 239000000312 peanut oil Substances 0.000 claims description 4
- 125000000547 substituted alkyl group Chemical group 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
- 238000005406 washing Methods 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
- 238000004821 distillation Methods 0.000 claims description 2
- 210000000582 semen Anatomy 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- 150000001298 alcohols Chemical class 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
- 229910021645 metal ion Inorganic materials 0.000 abstract 1
- 230000036632 reaction speed Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- 235000014113 dietary fatty acids Nutrition 0.000 description 11
- 229930195729 fatty acid Natural products 0.000 description 11
- 239000000194 fatty acid Substances 0.000 description 11
- 150000002194 fatty esters Chemical class 0.000 description 11
- 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
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007171 acid catalysis Methods 0.000 description 3
- 108010037444 diisopropylglutathione ester Proteins 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
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000011259 mixed solution 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
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012546 transfer 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
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-heterocycliccarbene-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, and conversion unit is expensive.
Ester exchange method converts full-bodied animal-plant oil and low-carbon alcohol generation transesterification reaction into fatty ester, 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; Must alcohol 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 corrosion on Equipment property.Yang Jianguo etc. (CN101250422) disclose a kind of biodiesel oil preparing process of solid acid catalysis, have reduced reaction process to corrosion on 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, Pottasium 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 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 one type of High-Efficient Organic catalyzer, 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; Comprising the process of Cabbeen alcohol adducts catalysis transesterify, some the Cabbeen alcohol adducts that relates to must just can discharge active Cabbeen in heating under the vacuum condition, has increased operation easier.N-heterocycle carbine carbon dioxide adduct is stable to empty G&W; Again can through change temperature, solvent controlled discharge active Cabbeen; As catalyzer; Store and use all very convenient because containing metal not in its molecule is difficult in product, introducing the metals ion that influences biodiesel quality.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, reactive behavior is high; Speed of response is fast, and reaction conditions is gentle relatively, does not introduce metals 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 after separating, obtains the product biofuel.
In above-mentioned preparation method of bio-diesel oil, the structural formula of said 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 said 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 one or more the substituted alkyl in halogen atom, hydroxyl, phenyl and the cyanic acid; Naphthenic base with 3～6 carbon atoms, phenyl or by the identical or different group in one or more the substituted phenyl in halogen atom, hydroxyl, alkyl and the cyanic acid; R
3, R
4Be selected from hydrogen; Halogen atom; Cyanic acid, hydroxyl has the alkyl of 1～4 carbon atom; Has 1～4 carbon atom and by one or more the substituted alkyl in halogen atom, hydroxyl, phenyl and the cyanic acid, phenyl or by the identical or different group in one or more the substituted phenyl in halogen atom, hydroxyl, alkyl and the cyanic acid.
In above-mentioned preparation method of bio-diesel oil, said vegetables oil is VT 18, Trisun Oil R 80, sweet oil, rapeseed oil, peanut oil, til, 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, said low-carbon alcohol is methyl alcohol, ethanol, n-propyl alcohol, Virahol or propyl carbinol.
In above-mentioned preparation method of bio-diesel oil,, low-carbon alcohol in pure oil mixt, adds solubility promoter when being methyl alcohol or ethanol.
In above-mentioned preparation method of bio-diesel oil, said solubility promoter is a THF, 1,4-dioxane, ether, DIPE 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 said 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, said temperature of reaction is 55～120 ℃, 2～100 minutes reaction times.
In above-mentioned preparation method of bio-diesel oil; Said separation method is that standing demix is isolated upper strata ester phase with the reaction solution washing; 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 metals ion, no equipment corrosion, and product postprocessing is simple.
Embodiment:
According to following embodiment, can understand the present invention better.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 explain the present invention, and the present invention that should also can not limit in claims to be described in detail.
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, with the uniform mixing (mol ratio is 1:6:7) of VT 18, methyl alcohol, THF; Add catalyst A (catalyzer be VT 18 quality 0.1%), stir termination reaction after 2 minutes; Steam unreacted methanol and THF, standing demix takes 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 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; Utilize the analysis of Agilent GC-7890A gas chromatograph, recording the fatty acid triglycercide transformation efficiency is 96%, and the fatty ester content of middle methyl esters mutually is 97%.
Embodiment 3
60 ℃ of temperature of reaction, under the nitrogen protection, with the uniform mixing liquid (mol ratio is 1:10:4) of peanut oil, methyl alcohol, THF; Add catalyzer C (catalyzer be peanut oil quality 1%), stir termination reaction after 30 minutes; Steam unreacted methanol and THF, standing demix takes 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 ester content of middle methyl esters mutually is 98%.
Embodiment 4
65 ℃ of temperature of reaction, under the nitrogen protection, with the uniform mixing liquid (mol ratio is 2:40:1) of sunflower seed oil, methyl alcohol, DIPE; Add catalyzer D (catalyzer be sunflower seed oil quality 3%), stir termination reaction after 30 minutes; Steam unreacted methanol and DIPE, standing demix takes 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 ester content of middle methyl esters mutually is 98%.
Embodiment 5
65 ℃ of temperature of reaction, under the nitrogen protection, with the uniform mixing liquid (mol ratio is 4:120:1) of soya-bean oil, methyl alcohol, THF; Add catalyzer E (catalyzer be soya-bean oil quality 5%), stir termination reaction after 30 minutes; Steam unreacted methanol and THF, standing demix takes 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 ester content of middle methyl esters mutually is 99%.
Embodiment 6
75 ℃ of temperature of reaction, under the nitrogen protection, with the uniform mixing liquid (mol ratio is 1:10:4) of VT 18, ethanol, ether; Add catalyzer F (catalyzer be VT 18 quality 1%), stir termination reaction after 30 minutes; Steam unreacted ethanol and ether, standing demix takes 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 ester content of middle ethyl ester mutually is 97%.
Embodiment 7
80 ℃ of temperature of reaction, under the nitrogen protection, with the uniform mixing liquid (mol ratio is 1:20:5) of Viscotrol C, ethanol, THF; Add catalyzer G (catalyzer be VT 18 quality 1%), stir termination reaction after 60 minutes; Steam unreacted ethanol and THF, standing demix takes 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 ester content of middle ethyl ester mutually is 97%.
Embodiment 8
100 ℃ of temperature of reaction, under the nitrogen protection, with the uniform mixing liquid (mol ratio is 1:10) of rapeseed oil, propyl alcohol; Add catalyzer H (catalyzer be rapeseed oil quality 1%), stir termination reaction after 60 minutes; Steam unreacted propyl alcohol, standing demix takes 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 ester content of middle propyl ester mutually is 95%.
Embodiment 9
85 ℃ of temperature of reaction, under the nitrogen protection, with the uniform mixing liquid (mol ratio is 1:10) of VT 18, Virahol; Add catalyst I (catalyzer be VT 18 quality 1%), stir termination reaction after 60 minutes; Steam unreacted Virahol, standing demix takes 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 ester content of middle isopropyl ester mutually is 96%.
Embodiment 10
120 ℃ of temperature of reaction, under the nitrogen protection, with the uniform mixing liquid (mol ratio is 1:10) of soya-bean oil, butanols; Add catalyzer J (catalyzer be VT 18 quality 1%), stir termination reaction after 100 minutes; Steam unreacted butanols, standing demix takes 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 ester content of middle butyl ester mutually is 93%.
Claims (10)
1. one kind prepares 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 after separating, obtains the product biofuel.
Wherein the mol ratio of vegetables oil and low-carbon alcohol is 1: 6～1: 30, and catalyst levels is 0.1%～5% of a vegetables oil quality, and temperature of reaction is 55～120 ℃, and the reaction times is 2～100 minutes.
2. a kind of preparation method of bio-diesel oil according to claim 1, the structural formula that it is characterized in that said 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 said 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 one or more the substituted alkyl in halogen atom, hydroxyl, phenyl and the cyanic acid; Naphthenic base with 3～6 carbon atoms, phenyl or by the identical or different group in one or more the substituted phenyl in halogen atom, hydroxyl, alkyl and the cyanic acid; R
3, R
4Be selected from hydrogen; Halogen atom; Cyanic acid, hydroxyl has the alkyl of 1～4 carbon atom; Has 1～4 carbon atom and by one or more the substituted alkyl in halogen atom, hydroxyl, phenyl and the cyanic acid, phenyl or by the identical or different group in one or more the substituted phenyl in halogen atom, hydroxyl, alkyl and the cyanic acid.
4. a kind of preparation method of bio-diesel oil according to claim 2 is characterized in that said vegetables oil is VT 18, Trisun Oil R 80, sweet oil, rapeseed oil, peanut oil, til, 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 said 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 said 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 said 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 said 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 said 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 standing demix is isolated upper strata ester phase with the reaction solution washing; Obtain product biofuel or distillation and remove unreacted low-carbon alcohol; Standing demix is isolated upper strata ester phase, obtains the product biofuel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102355934A CN101418226B (en) | 2008-12-01 | 2008-12-01 | Method for preparing biodiesel by using N-heterocyclic carbine carbondioxide adducts as catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102355934A CN101418226B (en) | 2008-12-01 | 2008-12-01 | Method for preparing biodiesel by using N-heterocyclic carbine carbondioxide adducts as catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101418226A CN101418226A (en) | 2009-04-29 |
| CN101418226B true CN101418226B (en) | 2012-01-25 |
Family
ID=40629232
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008102355934A Active CN101418226B (en) | 2008-12-01 | 2008-12-01 | Method for preparing biodiesel by using N-heterocyclic carbine carbondioxide adducts as catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101418226B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101085927A (en) * | 2006-06-08 | 2007-12-12 | 河南农业大学 | Method for catalytically synthesizing biological diesel oil by lipase |
-
2008
- 2008-12-01 CN CN2008102355934A patent/CN101418226B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101085927A (en) * | 2006-06-08 | 2007-12-12 | 河南农业大学 | Method for catalytically synthesizing biological diesel oil by lipase |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101418226A (en) | 2009-04-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ashokkumar et al. | Production of liquid biofuels (biodiesel and bioethanol) from brown marine macroalgae Padina tetrastromatica | |
| Fan et al. | Sulfonated imidazolium ionic liquid-catalyzed transesterification for biodiesel synthesis | |
| Fan et al. | Recent development of biodiesel feedstocks and the applications of glycerol: a review | |
| ES2662743T3 (en) | Process for preparing biodiesel with lipase and dehydration in a separate line | |
| CN103642579B (en) | A kind of method preparing biofuel with micro-algae | |
| CN102925287A (en) | Method for preparing biodiesel by biological-chemical catalytic coupling | |
| Encinar et al. | Sunflower oil transesterification with methanol using immobilized lipase enzymes | |
| CN112657557B (en) | Preparation method of Pd/MOF catalyst for catalytic hydrogenation upgrading of phenol | |
| CN103361166A (en) | Method for preparing bio-oil from microalgae through direct liquidation | |
| Panchal et al. | Synthesis of polymer based catalyst: Optimization and kinetics modeling of the transesterification of Pistacia chinensis oil with diethyl carbonate using acidic ionic liquids | |
| CN103173293A (en) | Method for preparing biodiesel by utilizing high-acid value oil | |
| CN101215475B (en) | Middle and low temperature preparation method for biological diesel oil by using plants fruits and seeds oil and special-purpose distillation tower for the same | |
| CN104212848A (en) | Microbial oil preparation method with biodiesel byproducts as carbon sources | |
| Panchal et al. | Process optimization using novel acidic ionic liquids and the kinetics modeling of methyl esters using Jatropha curcas oil with dimethyl carbonate | |
| CN101418226B (en) | Method for preparing biodiesel by using N-heterocyclic carbine carbondioxide adducts as catalyst | |
| CN101463264B (en) | Method for using stalk vector in pbiodiesel preparation by lipid pyrolysis | |
| Qi et al. | One-step production of biodiesel from waste cooking oil catalysed by SO 3 H-functionalized quaternary ammonium ionic liquid | |
| CN104498544A (en) | Method for producing biodiesel by microalgae fermentation | |
| CN101338215A (en) | Method for preparing biodiesel by catalyzing oil or fatty acid with solid | |
| CN101497803A (en) | Biodiesel and preparing technology thereof | |
| CN102154064B (en) | Preparation method of biodiesel | |
| CN100526427C (en) | Method and catalyst for producing biological diesel oil by high-acid value grease | |
| Gopinath et al. | Optimizing the various parameters for biodiesel production by transesterification | |
| CN102993005B (en) | Method for preparing fatty acid alkyl ester by using long-chain alkyl sulfonic acid functional polyoxometalate as catalyst | |
| KR101548043B1 (en) | Preparation method of biodiesel using microorganism |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C57 | Notification of unclear or unknown address | ||
| DD01 | Delivery of document by public notice |
Addressee: Li Zhenjiang Document name: Notification of Passing Preliminary Examination of the Application for Invention |
|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Guo Kai Inventor after: Li Zhenjiang Inventor after: Zhou Jixin Inventor after: Shi Qian Inventor after: Song Ping Inventor after: Qin Huimin Inventor after: Wei Ping Inventor after: Ouyang Pingkai Inventor before: Li Zhenjiang Inventor before: Zhou Jixin Inventor before: Shi Qian Inventor before: Song Ping Inventor before: Qin Huimin Inventor before: Wei Ping Inventor before: Ouyang Pingkai |