CN102586031A - Ion-liquid-based method for preparing biodiesel - Google Patents
Ion-liquid-based method for preparing biodiesel Download PDFInfo
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Abstract
The invention discloses an ion-liquid-based method for preparing biodiesel, which is characterized in that fats of animals and plants and methanol are used as raw materials, and sulfonate functionalized benzene sulfonate quaternary ammonium ionic liquid are used as a catalyst and a solubilizer. The catalyst can be used for simultaneously catalyzing ester interchange and esterification reactions and carrying out the ester interchange and esterification reactions in the same reactor to synthesize the biodiesel. The ion liquid-based method for preparing biodiesel has the characteristics of simple process, quick reaction speed and high conversion rate, the catalyst can be recycled, has low corrosivity and is green and environment-friendly, and thus the method has better industrial application prospect.
Description
Technical field
The invention belongs to technical field of green regenerative energy sources, be specifically related to a kind ofly prepare method of bio-diesel oil based on ionic liquid.
Background technology
Along with the exhaustion day by day of petroleum resources and the raising of human environmental consciousness, People more and more is paid close attention to oil-fired substitute.Biofuel is the fatty acid ester material that is generated through transesterify (or/and esterification) reaction by animal-plant oil (or/and lipid acid) and short chain alcohol; It is a kind of novel non-pollution of renewable energy; Its combustionproperty can match in excellence or beauty with traditional petrifaction diesel; But objectionable impurities reduces about 50% than petrifaction diesel in the tail gas that the burning rear engine gives off, and is one of ideal fuels that substitutes petrifaction diesel.
The production of biofuel mainly is to make through transesterification reaction is taken place under catalyst action for animal-plant oil (glyceryl ester) and short chain alcohol (methyl alcohol, ethanol etc.), also can make through esterification is taken place under catalyst action for lipid acid and short chain alcohol (methyl alcohol, ethanol etc.).According to the difference of use catalyzer, the working method of biofuel mainly contains two kinds of enzyme process and chemical methods.Short chain alcohol very easily causes enzyme deactivation in the enzyme process, and the easy surface attached to enzyme of the by-product glycerin of reaction generation, makes reaction be difficult to carry out.Traditional chemical method adopts strong acid (sulfuric acid) or highly basic (sodium hydroxide, Pottasium Hydroxide) to make catalyzer usually; Its reaction conditions is gentle, and speed of response is fast, but catalyzer has corrodibility; And after finishing, reaction needs catalyzer is neutralized; Catalyzer can not recycle and have sewage to discharge, and need carry out WWT, makes production cost increase.Though adopt heterogeneous solid acid or alkaline catalysts can overcome above deficiency, heterogeneous catalyst existence activity is low, speed of response is slow, catalyzer is prone to inactivation needs shortcomings such as repeated regeneration and regeneration cost height.Therefore, develop environment amenable green, fast new synthetic process has become the task of top priority.
Ionic liquid is as a kind of novel eco-friendly solvent and liquid acid catalyst, and have other organic and inorganic solvent and the not available advantage of traditional catalyst: it has the non-volatility of high-density reactive behavior, flowability and the solid acid of liquid acid simultaneously; Acidity can surpass solid super-strong acid, and acidity can be regulated as required; Catalyzer separates with product easily, and is environmentally friendly; Liquid journey wide ranges can reach 300-400 ℃; Has non-inflammability; Of a great variety, its physicochemical property depend on the kind of forming ion liquid zwitterion to a great extent, are truly programmable green solvent and catalyzer.
Therefore, the active height of exploitation, catalytic performance are stablized, the segregative ionic liquid-catalyzed preparation biofuel friendly process of product has caused great concern, and the Chinese invention patent of application existing ten is multinomial at present.
Zhang Suojiang etc. disclose a kind of " based on ion liquid method for synthesizing biologic diesel oil " in Chinese invention patent ZL200510082972.0; This method is with imidazole type ion liquid or such ionic liquid and common acidity or basic catalyst formation composite catalyst, through the transesterification reaction biodiesel synthesis.Ion liquid negatively charged ion comprises HSO
4 -, OH
-And H
2PO
4 -, common alkaline catalyst pack is drawn together: NaOH, Na
2CO
3, K
2CO
3, Na
2O, K
2O, RONa, ROK, an acidic catalyst comprises: H
2SO
4, H
3PO
4,
CH
3(CH
2)
11SO
3H,
Wu Qin etc. disclose " a kind of preparation method of bio-diesel oil " in application number is 200510086385.9 patent; This method is a raw material with bio-oils such as Viscotrol C, rapeseed oil, VT 18, peanut oil, Semen Maydis oil, fish oil, lard or algae greases; B acid ion liquid with the band sulfonate functional groups is catalyzer, and ion liquid positively charged ion comprises:
Negatively charged ion comprises: HSO
4 -, CF
3SO
3 -, NO
3 -, BF
4 -, PF
6 -, CH
3(C
6H
4) SO
3 -, Cl
-, H
2PO
4 -, C
nH
2n+1COO
-, N (C
2F
5SO
2)
2 -, C (CF
3SO
2)
3 -, C
nH
2n+1SO
3 -, CF
3COO
-
Han Minghan etc. also disclose " a kind of preparation method of bio-diesel oil " in application number is 200610083300.6 patent; This patent is further expanding of above-mentioned Wu Qin patent; Used ionic-liquid catalyst is identical with the Wu Qin patent; But but ionic liquid is except that catalyzed transesterification; Also but catalysis is that raw material prepares biofuel with pure esterification with lipid acid, and the bio-oil raw material of transesterification reaction has also increased tea oil, tung oil, oleum lini, plam oil and Oleum Gossypii semen, sweet oil, butter and catering trade waste grease etc.
Huang Baohua etc. disclose " a kind of prepare method of bio-diesel oil with microwave catalysis " in application number is 200810029722.4 patent; This method adopts microwave-assisted synthesis; Use vegetables oil or acidifying oil or useless food and drink oil or sewer oil and methyl alcohol or ethanol to be raw material, with the composite catalyst catalysis for preparing biodiesel oil of imidazoles alkali ionic liquid and alkali (NaOH or KOH) composition.Huang Baohua etc. also disclose " a kind of method of preparing biodiesel by sulfonic acid type ion liquid " in application number is 200810220576.3 patent; It is the catalyzer of transesterification reaction that this method adopts the pyrrolidinone compounds of acid sulfonic acid type or morphine quinoline class ionic liquid, is the feedstock production biofuel with VT 18, rapeseed oil, peanut oil, Oleum Verniciae fordii, Viscotrol C, Semen Maydis oil, Oleum Gossypii semen, Fructus Zanthoxyli oil, lard, fish oil or algae grease.
The big woodss of state etc. disclose " a kind of method of preparing biodiesel by synergic ion liquid catalysis under cavitation effect " in application number is 200810157645.0 patent; This method is a raw material with the waste oil of natural vegetables oil, animal oil or recovery; And earlier raw oil is removed free fatty acids and processed; Under the effect of cavitation effect, carry out the transesterification reaction biodiesel synthesis then; Catalyst system therefor is acidity or alkali ionic liquid; Or the composite catalyst of ionic liquids ionic liquids and acid or alkali formation, like the composite catalyst of ionic liquid and sulfuric acid, nitric acid, phosphoric acid, organic acid, solid acid, sodium hydroxide, Pottasium Hydroxide, sodium methylate, potassium methylate, yellow soda ash, salt of wormwood, quicklime or Natural manganese dioxide formation.Ionic liquid is the ionic liquid that at room temperature is liquefaction that alkyl imidazole, alkyl pyridine, quaternary ammonium salt 、 quaternary alkylphosphonium salt and metal or nonmetallic halogenide form.
Ceng Zheling etc. disclose a kind of " method of producing light biological diesel oil with seed oil of camphor " in application number is 200810107378.6 patent; This method is raw material with the camphor tree seed oil; Crude oil is after pre-treatment is come unstuck in removal of impurities; Earlier carry out esterification under to the ionic liquid-catalyzed effect of Methylimidazole acidifying, then at particulate supported type KOH/MgO/Al at sulfuric acid propyl sulfonic acid base
2O
3Katalysis under carry out transesterification reaction and make the light weight type biofuel.
Salty deserts etc. disclose " a kind of ionic liquid-catalyzed preparation method of bio-diesel oil " in application number is 200810057894.2 patent; This method is raw material with the free fatty acids; Under the sulfonic functional ion liquid katalysis, carry out esterification and prepare biofuel; Ion liquid positively charged ion comprises alkyl pyridine positively charged ion, the sulfonic functional 1 of sulfonic functional; 3-dialkylimidazolium positively charged ion and acidic group functionalization alkylamine salt positively charged ion, negatively charged ion comprises cl ions, fluoroboric acid root, bisulfate ion, tosic acid root and trifluoromethanesulfonic acid root.
Chen Ji etc. disclose a kind of hydroxyl type anion resin that contains glyoxaline structure and preparation method thereof in application number is 200910217977.8 patent, and are applied to catalysis soya-bean oil transesterification reaction and prepare biofuel.
Zhang Jianwang discloses a kind of " preparation method of bio-diesel oil with animal-plant oil and bright potato " in application number is the patent of 200910227842.X; This method is hydrolyzed into lipid acid with animal-plant oil earlier under the acid catalysis effect; And bright potato become ethanol through biological fermentation; In ionic liquid-catalyzed effect, lipid acid and ethanol generation esterification make biofuel then.Used ionic liquid has two kinds of 1-ethyl-3-methyl imidazolium tetrafluoroborate and N-N-methyl-2-2-pyrrolidone N-base methylsulfonic acids.
Chen Ligong discloses " a kind of technology of preparing biodiesel by food and beverage waste oil " in application number is 201010216784.3 patent; This technology dewaters waste cooking oil filtering and impurity removing and heating earlier, under the ion liquid katalysis of basic imidazole type, prepares biofuel with methyl alcohol or ethanol synthesis then.
Chen Xuerong etc. disclose " a kind of method of preparing biodiesel from tall oil " in application number is 201010213123.5 patent.Tall oil is compositions such as the regenerant of pine alkaline pulping black liquor, fatty acids, sylvic acid and sterol.This method is raw material with the tall oil, biodiesel synthesis under katalysis such as solid super-strong acid, zeolite molecular sieve, heteropolyacid and 1-hexadecyl-2,3 methylimidazole fluoroform sulphonate ionic liquid.
Wang Bo etc. disclose " a kind of biodiesel catalyst and the method for utilizing this biodiesel " in application number is 201010225684.7 patent; This method is a raw material with lipid acid, oleic acid, linolic acid, palmitinic acid, LAURIC ACID 99 MIN, linolenic acid, tetradecanoic acid or Triple Pressed Stearic Acid; With many sulfonate functionalizations ionic liquid; The ionic liquid that promptly contains 2 and above sulfonic functional is a catalyzer, through the esterification biodiesel synthesis.
Wang Haijuns etc. disclose the method for a kind of " the amino acid ion liquid catalytic transesterification prepares biofuel " in application number is 201010520436.5 patent; This method is raw material with the Viscotrol C; With the amino acid ion liquid is catalyzer, through the transesterification reaction biodiesel synthesis.Ion liquid positively charged ion is 1-butyl-3-Methylimidazole, and negatively charged ion is glycocoll root or glutamate.
Guo Feng etc. disclose " a kind of ionic liquid-catalyzed preparation method of bio-diesel oil " in application number is 201010578591.2 patent; This method is a raw material with high-acid value greases such as free fatty acids such as Triple Pressed Stearic Acid, oleic acid, linoleic acid plus linolenic acid or sewer oil, swill oil, frying waste oil, plant oil leftover or squeezing Jatropha curcas oils, prepares biofuel through esterification or transesterification reaction.The catalyzer of esterification is the mixture of imidazole type ion liquid or such ionic liquid and metal chloride; Ion liquid negatively charged ion comprises cl ions, bromide anion and toluenesulphonic acids radical ion; Metal chloride comprises Aluminum chloride anhydrous, anhydrous chlorides of rase platinum, Anhydrous Ferric Chloride, anhydrous cupric chloride, Manganese chloride anhydrous, anhyd chromic chloride and Zinc Chloride Anhydrous etc., and the catalyzer of transesterification reaction has alkaline catalystss such as Pottasium Hydroxide, sodium hydroxide, water glass, quicklime and magnesium aluminum-hydrotalcite.
But not seeing has with sulfonic functional Phenylsulfonic acid quaternary ammonium salt ionic liquid as catalyzer and solubilizing agent, through the technological invention or the academic research report of transesterify/esterification biodiesel synthesis.
Summary of the invention
The invention provides and a kind ofly prepare method of bio-diesel oil based on ionic liquid; Ionic liquid of the present invention has catalysis and solublization simultaneously; And simultaneously catalytic transesterification and esterification, can in same reactor drum, carry out transesterify and esterification biodiesel synthesis simultaneously.The present invention has that technology is simple, speed of response is fast, transformation efficiency is high, catalyzer is reusable, corrodibility is low, the characteristics of environmental protection, and good industrialized application prospect is arranged.
In order to reach above-mentioned purpose, solution of the present invention is:
A kind ofly prepare method of bio-diesel oil based on ionic liquid; With animal-plant oil (the high acid value grease that comprises fatty acids) and methyl alcohol is raw material; With sulfonic functional Phenylsulfonic acid quaternary ammonium salt ionic liquid as catalyzer and solubilizing agent, through transesterify/esterification biodiesel synthesis.
The ion liquid structure of said sulfonic functional Phenylsulfonic acid quaternary ammonium salt is A
+B
-,
Cation A
+Comprise:
Wherein to represent carbonatoms be the alkyl of 2-8 to R;
Negatively charged ion B
-For:
Described animal-plant oil comprises VT 18, rapeseed oil, peanut oil, Semen Maydis oil, Viscotrol C, plam oil, sweet oil, Oleum Gossypii semen, tea-seed oil, lard, butter, fish oil, algae grease and catering trade waste grease etc.
The ion liquid compound method of said sulfonic functional Phenylsulfonic acid quaternary ammonium salt is following:
The first step: with 1 of 0.2mol, 3-N-morpholinopropanesulfonic acid lactone and 20mL ETHYLE ACETATE (as solvent) mix in there-necked flask, dropwise add the amine of 0.2mol again, stir 1d down at 50 ℃, obtain white solid, and vacuum-drying makes midbody RN
+(CH
2)
3SO
3 -
Second step: with the midbody that makes with etc. the Phenylsulfonic acid of amount in there-necked flask, mix, and make solvent with ETHYLE ACETATE, at 50 ℃ of stirring 6h down, all dissolve, liquefy until zwitter-ion, be incubated 2h again.Post reaction mixture is changed in the single port bottle,, remove solvent ethyl acetate, place vacuum drying oven (design temperature is 70 ℃) drying at last, thoroughly remove and desolvate, make sulfonic functional Phenylsulfonic acid quaternary ammonium salt ionic liquid at 60 ℃ of following vacuum rotary steam 3h.
The mol ratio of described animal-plant oil and methyl alcohol is 1: 9-15, the ion liquid add-on of sulfonic functional Phenylsulfonic acid quaternary ammonium salt is the 0.06-0.15 of raw oil material molar weight.
Described transesterify/esterification reaction temperature is 60-140 ℃, and the reaction times is 2-24 hour.
After reaction finishes, standing demix, the upper strata is the biofuel phase, and glycerine, methyl alcohol and ionic liquid are contained in lower floor, and after methyl alcohol and glycerine were isolated in underpressure distillation respectively, ionic liquid was reusable.
Beneficial effect of the present invention is:, product aftertreatment big to the long reaction time that exists in the present biofuel industrial production, catalytic erosion property has problems such as sewage discharge; Solubilising and transesterify katalysis when utilizing sulfonic functional Phenylsulfonic acid quaternary ammonium salt ionic liquid that the present invention is ingenious to the biofuel synthetic system; Initial reaction stage particularly; Through utilizing ion liquid solublization; Promote the degree of dissolving each other of grease and methyl alcohol, can improve speed of reaction greatly, thereby fundamentally solve the slow problem of initial reaction stage speed of reaction; Another beneficial effect is: ionic liquid of the present invention can the catalysis grease and methyl alcohol between transesterification reaction; The esterification between catalysis lipid acid and the methyl alcohol simultaneously again; Therefore; For the raw material that contains grease and lipid acid simultaneously (like high-acid-value materials such as catering trade waste greases), the present invention makes biofuel as long as can realize transesterify and esterification simultaneously with a kind of catalyzer, in a reactor drum, and traditional technology then need be carried out preparatory esterification earlier and then carried out transesterify; The present invention promptly must adopt two step process, so can simplify the technology for preparing biofuel from high-acid-value material; Also have a beneficial effect to be: because the biofuel and the ionic liquid that generate are immiscible basically; Therefore the biofuel of reaction generation will be discharged to another phase; Reaction is constantly carried out with regard to not receiving the equilibrated constraint like this, thereby has improved the productive rate of greasy transformation efficiency and biofuel.Simultaneously, because ionic liquid and delamination of biodiesel, separate easily, so ionic liquid can be recycled, simultaneously because ionic liquid is insoluble to biofuel, so the product aftertreatment is simple, does not also have sewage to discharge.Owing to above reason; Make compound method of the present invention become a kind of can be in same reactor drum simultaneously catalytic transesterification and esterification, speed of response is fast, transformation efficiency is high, catalyst recovery is simple and reusable, economic benefit is high, the method for environmental protection.
With traditional method for synthesizing biologic diesel oil ratio, the present invention has the following advantages:
1) ionic liquid both as the medium of reaction, can promote the mutual solubility of grease and methyl alcohol to play the effect of solubilizing agent at the initial stage of reaction, again as the catalyzer of transesterify/esterification, and had higher acid catalysis activity.Ion liquid this while solubilising and katalysis can improve the synthesis rate of biofuel greatly.
2) ionic liquid of the present invention can the catalysis grease and methyl alcohol between transesterification reaction; The esterification between catalysis lipid acid and the methyl alcohol simultaneously again; Therefore; For the raw material that contains grease and lipid acid simultaneously, as long as the present invention is with a kind of catalyzer, in a reactor drum, transesterification reaction and esterification are carried out simultaneously and make biofuel, thereby changes the earlier preparatory esterification of the traditional need two step process of transesterify again; Technology is become simply, and can save facility investment and process cost.
3) ionic liquid has steam and forces down, cleans characteristics such as nontoxic, thus use do not have volatilization, pollution-free, corrodibility is little, is a kind of green, free of contamination solvent and catalyzer.And, after the reaction methyl alcohol and the glycerine of ionic liquid in mutually to be separated, ionic liquid uses with regard to recyclable cycle repeats.
Embodiment
Embodiment 1
With 1 of 0.2mol, 3-N-morpholinopropanesulfonic acid lactone and 20mL ETHYLE ACETATE (as solvent) mix in there-necked flask, dropwise add the triethylamine of 0.2mol again, stir 1d down at 50 ℃, obtain white solid, and vacuum-drying makes midbody; The 0.1mol midbody is mixed in there-necked flask with the Phenylsulfonic acid of 0.1mol, and make solvent, stir 6h down, all dissolve, liquefy, be incubated 2h again until zwitter-ion at 50 ℃ with ETHYLE ACETATE.Post reaction mixture is changed in the single port bottle,, remove solvent ethyl acetate, place vacuum drying oven (design temperature is 70 ℃) drying at last, thoroughly remove and desolvate, make triethylamine propane sulfonic acid benzene sulfonate ionic liquid at 60 ℃ of following vacuum rotary steam 3h.
In the 100mL glass there-necked flask of stirring, TM, prolong is housed; Add 5.7658g (about 0.18mol) methyl alcohol and 1.2742g (about 0.00334mol) triethylamine propane sulfonic acid benzene sulfonate ionic liquid; The dissolving back adds 17.6000g (about 0.02mol) VT 18; Setting temperature of reaction is 60 ℃, and condensing reflux is heated in oil bath, reacts to stop heating, stirring after 24 hours.The taking-up mixture places the separating funnel standing demix after being cooled to room temperature; The upper strata is a biofuel; Productive rate can reach 92%, and lower floor is the mixture of ionic liquid and methyl alcohol and by-product glycerin, after methyl alcohol and glycerine are isolated in underpressure distillation respectively; Remaining is ionic liquid, can overlap to use to react to recycle next time.
Embodiment 2
With 1 of 0.2mol, 3-N-morpholinopropanesulfonic acid lactone and 20mL ETHYLE ACETATE (as solvent) mix in there-necked flask, dropwise add the dibutylamine of 0.2mol again, stir 1d down at 50 ℃, obtain white solid, and vacuum-drying makes midbody; The 0.1mol midbody is mixed in there-necked flask with the Phenylsulfonic acid of 0.1mol, and make solvent, stir 6h down, all dissolve, liquefy, be incubated 2h again until zwitter-ion at 50 ℃ with ETHYLE ACETATE.Post reaction mixture is changed in the single port bottle,, remove solvent ethyl acetate, place vacuum drying oven (design temperature is 70 ℃) drying at last, thoroughly remove and desolvate, make dibutylamine propane sulfonic acid benzene sulfonate ionic liquid at 60 ℃ of following vacuum rotary steam 3h.
In the autoclave of 1L, add 76.877g (about 2.4mol) methyl alcohol and 6.8414g (about 0.0167mol) dibutylamine propane sulfonic acid benzene sulfonate ionic liquid, the dissolving back adds 177.800g (about 0.2mol) peanut oil; Setting temperature of reaction is 120 ℃, reacts to stop heating, stirring after 3 hours, takes out mixture after logical water quench to the room temperature and places the separating funnel standing demix; The upper strata is a biofuel; Productive rate can reach 95%, and lower floor is the mixture of ionic liquid and methyl alcohol and by-product glycerin, after methyl alcohol and glycerine are isolated in underpressure distillation respectively; Remaining is ionic liquid, can overlap to use to react to recycle next time.
Embodiment 3
With 1 of 0.2mol, 3-N-morpholinopropanesulfonic acid lactone and 20mL ETHYLE ACETATE (as solvent) mix in there-necked flask, dropwise add the Tributylamine of 0.2mol again, stir 1d down at 50 ℃, obtain white solid, and vacuum-drying makes midbody; The 0.1mol midbody is mixed in there-necked flask with the Phenylsulfonic acid of 0.1mol, and make solvent, stir 6h down, all dissolve, liquefy, be incubated 2h again until zwitter-ion at 50 ℃ with ETHYLE ACETATE.Post reaction mixture is changed in the single port bottle,, remove solvent ethyl acetate, place vacuum drying oven (design temperature is 70 ℃) drying at last, thoroughly remove and desolvate, make Tributylamine propane sulfonic acid benzene sulfonate ionic liquid at 60 ℃ of following vacuum rotary steam 3h.
In the 100mL glass there-necked flask of stirring, TM, prolong is housed; Add 5.7658g (about 0.18mol) methyl alcohol and 1.5534g (about 0.0033mol) Tributylamine propane sulfonic acid benzene sulfonate ionic liquid; The dissolving back adds 16.1464g (about 0.02mol) plam oil; Setting temperature of reaction is 60 ℃, and condensing reflux is heated in oil bath, reacts to stop heating, stirring after 20 hours.The taking-up mixture places the separating funnel standing demix after being cooled to room temperature; The upper strata is a biofuel; Productive rate can reach 91%, and lower floor is the mixture of ionic liquid and methyl alcohol and by-product glycerin, after methyl alcohol and glycerine are isolated in underpressure distillation respectively; Remaining is ionic liquid, can overlap to use to react to recycle next time.
Embodiment 4
With 1 of 0.2mol, 3-N-morpholinopropanesulfonic acid lactone and 20mL ETHYLE ACETATE (as solvent) mix in there-necked flask, dropwise add the trioctylamine of 0.2mol again, stir 1d down at 50 ℃, obtain white solid, and vacuum-drying makes midbody; The 0.1mol midbody is mixed in there-necked flask with the Phenylsulfonic acid of 0.1mol, and make solvent, stir 6h down, all dissolve, liquefy, be incubated 2h again until zwitter-ion at 50 ℃ with ETHYLE ACETATE.Post reaction mixture is changed in the single port bottle,, remove solvent ethyl acetate, place vacuum drying oven (design temperature is 70 ℃) drying at last, thoroughly remove and desolvate, make trioctylamine propane sulfonic acid benzene sulfonate ionic liquid at 60 ℃ of following vacuum rotary steam 3h.
In the autoclave of 1L, add 76.877g (about 2.4mol) methyl alcohol and 10.5876g (about 0.0167mol) trioctylamine propane sulfonic acid benzene sulfonate ionic liquid, the dissolving back adds 178.2980g (about 0.2mol) butter; Setting temperature of reaction is 140 ℃, and reacting by heating stops heating, stirs after 2 hours, takes out mixture after logical water quench to the room temperature and places the separating funnel standing demix; The upper strata is a biofuel; Productive rate can reach 95%, and lower floor is the mixture of ionic liquid and methyl alcohol and by-product glycerin, after methyl alcohol and glycerine are isolated in underpressure distillation respectively; Remaining is ionic liquid, can overlap to use to react to recycle next time.
Embodiment 5
With 1 of 0.2mol, 3-N-morpholinopropanesulfonic acid lactone and 20mL ETHYLE ACETATE (as solvent) mix in there-necked flask, dropwise add the diethylamine of 0.2mol again, stir 1d down at 50 ℃, obtain white solid, and vacuum-drying makes midbody; The 0.1mol midbody is mixed in there-necked flask with the Phenylsulfonic acid of 0.1mol, and make solvent, stir 6h down, all dissolve, liquefy, be incubated 2h again until zwitter-ion at 50 ℃ with ETHYLE ACETATE.Post reaction mixture is changed in the single port bottle,, remove solvent ethyl acetate, place vacuum drying oven (design temperature is 70 ℃) drying at last, thoroughly remove and desolvate, make diethylamine propane sulfonic acid benzene sulfonate ionic liquid at 60 ℃ of following vacuum rotary steam 3h.
In the 100mL glass there-necked flask of stirring, TM, prolong is housed; Add 5.7658g (about 0.18mol) methyl alcohol and 1.22748g (about 0.00334mol) diethylamine propane sulfonic acid benzene sulfonate ionic liquid; The dissolving back adds 13.1396g (about 0.03mol) algae grease; Setting temperature of reaction is 60 ℃, and condensing reflux is heated in oil bath, reacts to stop heating, stirring after 24 hours.The taking-up mixture places the separating funnel standing demix after being cooled to room temperature; The upper strata is a biofuel; Productive rate can reach 92%, and lower floor is the mixture of ionic liquid and methyl alcohol and by-product glycerin, after methyl alcohol and glycerine are isolated in underpressure distillation respectively; Remaining is ionic liquid, can overlap to use to react to recycle next time.
Embodiment 6
With 1 of 0.2mol, 4-butyl sultone and 20mL ETHYLE ACETATE (as solvent) mix in there-necked flask, dropwise add the trihexylamine of 0.2mol again, stir 1d down at 50 ℃, obtain white solid, and vacuum-drying makes midbody; The 0.1mol midbody is mixed in there-necked flask with the Phenylsulfonic acid of 0.1mol, and make solvent, stir 6h down, all dissolve, liquefy, be incubated 2h again until zwitter-ion at 50 ℃ with ETHYLE ACETATE.Post reaction mixture is changed in the single port bottle,, remove solvent ethyl acetate, place vacuum drying oven (design temperature is 70 ℃) drying at last, thoroughly remove and desolvate, make trihexylamine butane sulfonic acid benzene sulfonate ionic liquid at 60 ℃ of following vacuum rotary steam 3h.
In the autoclave of 1L; Catering trade abendoned oil after adding 76.877g (about 2.4mol) methyl alcohol and 7.5402g (about 0.0167mol) trihexylamine butane sulfonic acid benzene sulfonate ionic liquid, dissolving back adding 168.0400g (about 0.2mol) are mixed through filtering and heating dewaters, setting temperature of reaction is 100 ℃; Reacting by heating stops heating, stirs after 4 hours; Take out mixture after logical water quench to the room temperature and place the separating funnel standing demix, the upper strata is a biofuel, and productive rate can reach 94%; Lower floor is the mixture of ionic liquid and methyl alcohol and by-product glycerin; After methyl alcohol and glycerine were isolated in underpressure distillation respectively, remaining was ionic liquid, can overlap to use to react to recycle next time.
Claims (8)
1. one kind prepares method of bio-diesel oil based on ionic liquid; It is characterized in that: with animal-plant oil and methyl alcohol is raw material; With sulfonic functional Phenylsulfonic acid quaternary ammonium salt ionic liquid as catalyzer and solubilizing agent, through transesterify/esterification biodiesel synthesis.
2. as claimed in claim 1ly a kind ofly prepare method of bio-diesel oil based on ionic liquid, it is characterized in that: ionic liquid physical efficiency catalyzing glycerol ester and methyl alcohol carry out transesterification reaction, and also catalysis lipid acid and methyl alcohol carry out esterification and generates biofuel simultaneously.
3. as claimed in claim 1ly a kind ofly prepare method of bio-diesel oil based on ionic liquid, it is characterized in that: the esterification of the transesterification reaction of glyceryl ester and methyl alcohol and lipid acid and methyl alcohol can be carried out in same reactor drum.
4. as claimed in claim 1ly a kind ofly prepare method of bio-diesel oil based on ionic liquid, it is characterized in that: the ion liquid structure of said sulfonic functional Phenylsulfonic acid quaternary ammonium salt is A
+B
-,
The ion liquid structure of said sulfonic functional Phenylsulfonic acid quaternary ammonium salt is A
+B
-,
Cation A
+Comprise:
Wherein to represent carbonatoms be the alkyl of 2-8 to R;
Negatively charged ion B
-For:
5. as claimed in claim 1ly a kind ofly prepare method of bio-diesel oil based on ionic liquid, it is characterized in that: described animal-plant oil comprises VT 18, rapeseed oil, peanut oil, Semen Maydis oil, Viscotrol C, plam oil, sweet oil, Oleum Gossypii semen, tea-seed oil, lard, butter, fish oil, algae grease and catering trade waste grease etc.
6. as claimed in claim 1ly a kind ofly prepare method of bio-diesel oil based on ionic liquid; It is characterized in that: described animal-plant oil is 1 with the mol ratio ratio of methyl alcohol: 9-15, the ion liquid add-on of sulfonic functional Phenylsulfonic acid quaternary ammonium salt is the 0.06-0.15 of raw oil material molar weight.
7. as claimed in claim 1ly a kind ofly prepare method of bio-diesel oil based on ionic liquid, it is characterized in that: described transesterify/esterification reaction temperature is 60-140 ℃, and the reaction times is 2-24 hour.
8. as claimed in claim 1ly a kind ofly prepare method of bio-diesel oil based on ionic liquid; It is characterized in that: after reaction finishes; Standing demix, upper strata are the biofuel phases, and glycerine, methyl alcohol and ionic liquid are contained in lower floor; After methyl alcohol and glycerine were told in underpressure distillation respectively, ionic liquid was reusable.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102872911A (en) * | 2012-10-23 | 2013-01-16 | 吴峰 | Ion liquid catalyst and fatty acid preparation method |
| CN102872911B (en) * | 2012-10-23 | 2015-04-08 | 吴峰 | Fatty acid preparation method |
| CN103131540A (en) * | 2013-02-19 | 2013-06-05 | 华侨大学 | Method for preparing biodiesel based on ionic liquid catalyzing peracid value rice bran oil |
| CN104694259A (en) * | 2015-02-13 | 2015-06-10 | 中国科学院广州能源研究所 | Method for preparing biodiesel by homogeneous catalysis of solubilizing and segregative ionic liquid |
| CN104694259B (en) * | 2015-02-13 | 2017-08-22 | 中国科学院广州能源研究所 | A kind of method that solubilized easily separated ionic liquid homogeneous catalysis prepares biodiesel |
| CN104774694A (en) * | 2015-04-08 | 2015-07-15 | 郑州凯山生化工程有限公司 | Method for synchronously preparing biodiesel and glycerol from high-acid-value vegetable oil |
| CN104804877A (en) * | 2015-04-15 | 2015-07-29 | 上海应用技术学院 | Pure biodiesel and preparation method thereof |
| CN108728249A (en) * | 2018-06-15 | 2018-11-02 | 成都恒润高新科技股份有限公司 | A method of preparing biodiesel using swill |
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