CN103265490A - Caprolactam basic ionic liquid as well as preparation method and application thereof - Google Patents
Caprolactam basic ionic liquid as well as preparation method and application thereof Download PDFInfo
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- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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Abstract
The invention discloses a method for preparing biodiesel by catalyzing waste oil with a caprolactam basic ionic liquid and belongs to the technical field of ionic liquid catalysis. According to the method for preparing the biodiesel by catalyzing waste oil with the caprolactam basic ionic liquid, the waste oil and alkyl alcohol are taken as raw materials, and the caprolactam basic ionic liquid is taken as a catalyst to prepare the biodiesel; and after reaction is finished, the ionic liquid and products are subjected to phase split automatically. The method for preparing the biodiesel by catalyzing waste oil with the caprolactam basic ionic liquid is simple in preparation process and low in cost. The method for preparing the biodiesel by catalyzing waste oil with the caprolactam basic ionic liquid has the advantages that firstly activity of the catalyst is high, and less catalyst is used; secondly, the catalyst is low in toxicity and can be easily biologically degraded; thirdly, reaction conditions are mild, and reaction time is short; and fourthly a reaction process is simple, products are easy to separate, no pollution is produced, and raw material utilization rate is high.
Description
Technical field
The present invention relates to ionic liquid-catalyzed technical field, especially hexanolactam class ionic liquid.
Background technology
Biofuel refers to that the cleaning that can be used for self-igniton engine of producing with renewable biological source such as plant, animal grease substitutes fuel oil.Biofuel have the cetane value height, substantially not sulfur-bearing and aromatic hydrocarbons, energy density height, lubricity is good, anti-knocking property are good, can biological degradation, advantage such as renewable, security height, partly or entirely alternative ore diesel oil uses.Preparation process is to react and get in liquid base (KOH, NaOH etc.) katalysis with raw material such as plant, animal grease and alcohols, but needs the liquid base in the repetitive scrubbing product, and therefore, the industrial sewage that process produces is many.
Ionic liquid refers to the salt compounds that at room temperature is in a liquid state, and it is made up of ion fully, is also referred to as " ionic liquid at room temperature ".Compared to traditional catalyst, ionic liquid has many unrivaled advantages, and the solvability of ionic liquid is good, can dissolve multiple organic solvent, has the dual-use function of solvent and catalyzer concurrently, reuses repeatedly, and catalytic effect does not subtract; Have liquid range preferably, between-100-300 ℃, all can keep liquid, helpful for dynamics research; Designability is strong, by the functionalized design to zwitterion, can regulate potential of hydrogen and solvability; Good stability, not volatile, can be used as the stationary phase of high performance liquid chromatography.Aspects such as ionic liquid has been successfully applied to chemosynthesis and has separated, electrochemistry, organic polymer, its application prospect is very wide.
US2009270248 patented invention content relates to a kind of novel alkali ionic liquid [Cat
+-Z-Bas] [X#x2212; ], Cat wherein
+=cationic moiety, the Bas=basic moiety, Z=connects Cat
+Covalent linkage with Bas; Perhaps 1,2 or 3 aliphatic divalent linker, each described aliphatic divalent linker all comprise 1 to 10 carbon atom and optionally comprise 1, two or 3 Sauerstoffatoms; The X#x2212=anionicsite, and condition is that Bas is not-OH.Its basic moiety is showed by positively charged ion, the catalysis that is designed to according to reaction environment to adapt to chemical process with efficient manner with separate, than conventional solvent system, the ionic liquid of this invention has low vapour pressure, adjustable polarity and performance and high thermostability.And the reaction with alkylogen and excessive diazabicyclo [2,2,2] octane obtains the ionic liquid of alkaline series.
Southern Yangtze University has introduced a kind of new double-core alkali ionic liquid and has prepared method of bio-diesel oil in patent CN102492559A.Described alkaline ionic liquid catalyst is two-(3-methyl isophthalic acid-imidazoles) ethylene oxyhydroxide, two-(3-methyl isophthalic acid-imidazoles) propylidene dihydroxide, two-(3-methyl isophthalic acid-imidazoles) butylidene dihydroxide, two-(3-methyl isophthalic acid-imidazoles) inferior heptyl dihydroxide, two-(3-methyl isophthalic acid-imidazoles) octylene dihydroxide.
Tropical plants garden, Chinese Academy of Sciences Xishuangbanna discloses a kind of 1-butyl-3-Methylimidazole tosilate, 1-octadecyl-3-Methylimidazole bromine salt, the 1-allyl group-pre-esterification waste oils of acidic ion liquid such as 3-Methylimidazole villaumite in patent CN102031202A, carry out transesterification reaction with potassium hydroxide, sodium hydroxide, calcium oxide or magnesium aluminum-hydrotalcite class alkaline catalysts again and prepare biofuel.
It is cationic ionic liquid and preparation method thereof with quaternised caprolactam that Lanzhou Inst. of Chemical Physics, Chinese Academy of Sciences discloses a kind of in patent CN1978431A.Make ionic liquid by hexanolactam and sulphonate by the single stage method reaction, and investigated ionic liquid to the stable of water and air and given prominence to the superior of its enthalpy change and thermostability, this ionic liquid is compared to glyoxaline ion liquid, raw material be easy to get and production cost low, product is pollution-free, and its liquid crystal property is better.
The CN101856512 patent disclosure a kind of basic imidazole class alkali ionic liquid catalysis food and beverage waste oil and grease prepare the technology of biofuel, the molecular formula of alkaline ionic liquid catalyst is:
This invention mainly is after waste oil is dewatered, alkali ionic liquid be catalyzer in the presence of, carry out esterification with methyl alcohol, product reclaims methyl alcohol through distillation, saturated sodium-chloride is washed behind the thick ester with hot water wash to neutral, adds to dewater at last and remembers refined biometric diesel oil.This technological operation is simple, the reaction conditions gentleness, but this technology cost is higher, and the industrial value of imidazoles is higher.
Changzhou University has announced a kind of with the ionic liquid-catalyzed method for preparing polyoxymethylene dimethyl ether of hexanolactam class in patent CN102120728A.Its general structure is as follows,
Wherein m represents 0 to 8 integer, and we select m=0,3 or 4 usually; X-is bisulfate ion, dihydrogen phosphate, p-methyl benzenesulfonic acid root, trifluoromethayl sulfonic acid root, a kind of in methylsulphonic acid root, trifluoroacetic acid root, formate, the acetate.By regulating the kind of negatively charged ion, the ionic liquid of preparation different acidity, and synthetic ionic liquid easily degrades compared to imidazoles, pyridines ionic liquid, and environment more is added with, and reusability is strong.Though the hexanolactam class ionic liquid of this patent prepares the catalysis waste oil in the reaction of biofuel certain catalytic activity is arranged also, effect is relatively poor.
Changzhou University has announced that in patent CN103013680A a kind of difunctional ionic liquid one-step catalytic waste oil prepares method of bio-diesel oil, and its general structure is:
Wherein R is-CH
3,-CH
2CH
3,-CH
2CH
2CH
3,-CH
2CH
2CH
2CH
3Or-CH
2CH
2CH
2CH
2CH
3Morpholine class ionic liquid is expensive as the catalyzer price that the catalysis waste oil prepares biofuel.
Changzhou University has announced that in patent CN103031217A a kind of pyrrolidinone compounds alkali ionic liquid catalysis waste oil prepares method of bio-diesel oil.Its general structure is
Wherein n represents 1～8 integer, and R is the alkyl of H or C1～C12, and hydroxyethyl or vinyl are selected n=1,2,3,4 or 5 alkyl substituent usually.Under the condition of this ionic liquid, overcome tradition and be reflected at shortcomings such as catalyzer is serious to equipment corrosion, speed of reaction is slow, the time is long, energy consumption is big, yield is low, and activity of such catalysts is higher, reaction process simple, product separates advantages such as easy, pollution-free.But compared to ionic liquid of the present invention, its productive rate is lower, and price does not have hexanolactam class ionic liquid cheap yet.
Summary of the invention
In view of existing acid hexanolactam class ionic liquid that the catalysis waste oil is prepared the not high problem of biofuel activity in the prior art, providing a kind of has double-function catalyzing and (namely can be used as catalyzer and can be used as solvent again, while catalytic esterification and transesterify two-step reaction) active hexanolactam class alkali ionic liquid, the one-step catalytic waste oil prepares the technical study method of biofuel.Thinking of the present invention is that to adopt waste oil and alkyl alcohol be raw material, and selecting hexanolactam class alkali ionic liquid is catalyzer, has reduced production cost and product is easily degraded, under mild conditions, and catalytically synthesizing biological diesel oil, catalytic activity height.
A kind of hexanolactam class alkali ionic liquid, its general formula is:
Wherein n is the integer of 1-8, and R is H or C
1-C
12Alkyl.
As preferably, n=1～5.
The preparation method of the above-mentioned hexanolactam class alkali ionic liquid of stating, step is as follows:
(1) hexanolactam class material and halogenated alkane in solvent at N
2Synthetic intermediate in the atmosphere is at N
2Improved purity and the productive rate of intermediate under the atmosphere condition greatly, described intermediate is through ethyl acetate and its unreacted solution of ether flush away, and rotary evaporation further obtains the higher intermediate of purity;
(2) again intermediate is dissolved in the methyl alcohol, obtains hexanolactam class ionic liquid with inorganic alkali alcosol prepared in reaction again.
As preferably, the described hexanolactam class of step (1) material comprises any one in hexanolactam, N-methyl caprolactam, N-ethyl hexanolactam, N-propyl group hexanolactam or the N-butyl hexanolactam.
As preferably, the described haloalkane of step (1) is C
1-C
8Bromo alkane, comprise a kind of in bromic ether, 1-bromo propane, bromination of n-butane or the 1-bromo pentane; Hexanolactam class material and haloalkane mol ratio are 1:0.5～2; Described solvent comprises a kind of in ethanol, acetonitrile or the toluene; Solvent quality is the 10%-50% of hexanolactam class material mass, and the amount of solvent influences the intermediate productive rate very little, and excessive solvent is unfavorable for aftertreatment, has also increased reaction cost; Described synthetic intermediate temperature of reaction is 70～120 ℃, reaction 4～12h.
As preferably, the described hexanolactam class of step (1) material is hexanolactam; Described halohydrocarbon is bromination of n-butane; Described solvent is acetonitrile, and solvent selects acetonitrile can improve the productive rate of intermediate compared to other solvents.
As preferably, the described intermediate of step (2) is dissolved in methyl alcohol, and methyl alcohol is 1～4ml/g with intermediate volume mass ratio;
The described mineral alkali of step (2) comprises NaOH, KOH, NaHCO
3,, KHCO
3Or Ca (OH)
2A kind of or at least two kinds of mixtures wherein; Because intermediate will react with inorganic alkali alcosol, in order not introduce the processing minimizing impurity interference that new solvent is the back, it is stronger to consider that again water-absorbent is put forward in its centre, prepare ionic liquid and carry out anionresin with its mineral alkali again, so mineral alkali is selected inorganic alkali alcosol for use, wherein alcohol is as solvent, consider that its pure polarity separates with bromine salt behind the synthetic ionic liquid the mineral alkali solvability with it, so described alcohol is selected methyl alcohol, methyl alcohol is 5～8ml/g with mineral alkali volume mass ratio;
The reaction mol ratio of described mineral alkali and intermediate is 0.9～1.5:1, and at room temperature the reaction times is 12～28h.
The application that above-mentioned hexanolactam class alkali ionic liquid catalysis waste oil prepares biofuel.
As preferably, waste oil as catalyzer, prepares biofuel with alkyl alcohol by esterification and transesterification reaction with ionic liquid.
As preferably, described waste oil comprises the wherein a kind of of acidifying oil, sewer oil, hogwash fat, swill oil; Ionic liquid is 2%～10% of waste oil quality; Described alkyl alcohol comprises the wherein a kind of or at least two kinds of mixtures in methyl alcohol, ethanol, Virahol, propyl carbinol, the primary isoamyl alcohol, and the alkyl alcohol consumption is 10%～40% of waste oil quality; Described esterification and transesterification reaction temperature are 40～120 ℃, and the reaction times is 1～5h.
Advantage of the present invention is:
1, the hexanolactam class alkali ionic liquid of the present invention's preparation is that catalyzer purity and productive rate are higher;
2, hexanolactam class alkali ionic liquid of the present invention is that catalyzer is active high as the catalyst that the catalysis waste oil prepares biofuel, and the transformation efficiency of waste oil is higher;
3, selected ionic liquid synthesis condition gentleness, reaction times are short, and the more glyoxaline ion liquid cost of the more current use of cost is low, can be applicable in the industrial production;
4, selected ionic liquid has wide temperature range, and alkalescence is strong, toxicity is low;
5, raw material availability height, catalyst levels is few, the automatic phase-splitting of post catalyst reaction and product;
6, catalytic reaction condition gentleness, temperature 40-120 ℃; Reactions steps is simple, and is easy to control;
7, catalyzer is synthetic simple, and cost is low, and is pollution-free, and reusable 8 times, the reaction after product is handled simple;
8, there are not problems such as etching apparatus and environmental pollution in catalyzer, the production process environmental protection, and cost of investment is lower;
9, have higher thermostability, not volatile.
Embodiment
Embodiment 1:
Taking by weighing the 10gN-methyl caprolactam is dissolved in and puts into four-hole boiling flask in the alcohol solvent, the ethanol consumption is 10% of N-methyl caprolactam quality, place oil bath pan to be warming up to 70 ℃, take by weighing bromination of n-butane in the constant voltage separating funnel, N-methyl caprolactam and bromination of n-butane mol ratio are 1:0.8, the control rate of addition slowly splashes into flask, feeds N simultaneously
2Insert prolong, thermometer, unlatching stirring, drip and finished to take out constant voltage separating funnel continuation stirring reaction 4 hours, reaction finishes to pour out the unreacted solution in upper strata, with ethyl acetate washing intermediate for several times, rotary evaporation is put into 70 ℃ of vacuum drying ovens and is dried to constant weight and namely obtain the higher intermediate of purity.Take by weighing intermediate in there-necked flask, add the solvent methanol wiring solution-forming, the methyl alcohol that adds is 1mL/g with intermediate volume mass ratio, take by weighing the methanol solution of KOH again, wherein methyl alcohol is 8mL/g with the volume mass ratio of mineral alkali, KOH and intermediate mol ratio are 0.9:1, at room temperature react 12h, suction filtration is removed the KBr solid, filtrate is revolved to steam and is removed most of methyl alcohol, add the ether recrystallization and separate out unreacted solution KOH and KBr, revolve and steam final vacuum and be dried to constant weight and namely obtain the higher ionic liquid of purity (ionic liquid 4).Carry out the thermogravimetric analysis heat decomposition temperature on the TG-DSC simultaneous thermal analysis and reach about 230 ℃, reach 89.94% through gas chromatographic analysis purity, productive rate reaches 90.02%.The infrared analysis data get: ionic liquid 2941.5,2497.4,1680.8,1413.0cm
-1Near C-H, N-H, C=O, C-N stretching vibration peak on the hexanolactam ring, 3200～3400cm appear respectively
-1Wide and the strong absorption peak that the district occurs is the hydroxyl absorption peak of ionic liquid.
Embodiment 2
Taking by weighing the 10g hexanolactam is dissolved in and puts into four-hole boiling flask in the acetonitrile solvent, the acetonitrile consumption is 50% of quality of caprolactam, place oil bath pan to be warming up to 120 ℃, take by weighing methyl bromide in the constant voltage separating funnel, hexanolactam and methyl bromide mol ratio are 1:2, the control rate of addition slowly splashes into flask, feeds N simultaneously
2Insert prolong, thermometer, unlatching stirring, drip and finished to take out constant voltage separating funnel continuation stirring reaction 12 hours, reaction finishes to pour out the unreacted solution in upper strata, with ethyl acetate washing intermediate for several times, rotary evaporation is put into 70 ℃ of vacuum drying ovens and is dried to constant weight and namely obtain the higher intermediate of purity.Take by weighing intermediate in there-necked flask, add the solvent methanol wiring solution-forming, the methyl alcohol that adds is 4mL/g with intermediate volume mass ratio, take by weighing the methanol solution of NaOH again, wherein methyl alcohol is 5mL/g with the volume mass ratio of mineral alkali, NaOH and intermediate mol ratio are 1.5:1, at room temperature react 28h, suction filtration is removed the NaBr solid, filtrate is revolved to steam and is removed most of methyl alcohol, adds the ether recrystallization and separates out unreacted solution NaOH and NaBr, revolves to steam final vacuum and be dried to constant weight and namely obtain the higher ionic liquid of purity (ionic liquid 1), thermogravimetric reaches 92.36% through the purity of gas chromatographic analysis gained ionic liquid, and productive rate reaches 94.83%.
Embodiment 3
Taking by weighing 10gN-ethyl hexanolactam is dissolved in and puts into four-hole boiling flask in the acetonitrile solvent, the acetonitrile consumption is 30% of quality of caprolactam, place oil bath pan to be warming up to 110 ℃, take by weighing bromination of n-butane in the constant voltage separating funnel, N-ethyl hexanolactam and bromination of n-butane mol ratio are 1:1, the control rate of addition slowly splashes into flask, feeds N simultaneously
2Insert prolong, thermometer, unlatching stirring, drip and finished to take out constant voltage separating funnel continuation stirring reaction 8 hours, reaction finishes to pour out the unreacted solution in upper strata, with ethyl acetate washing intermediate for several times, rotary evaporation is put into 70 ℃ of vacuum drying ovens and is dried to constant weight and namely obtain the higher intermediate of purity.Take by weighing intermediate in there-necked flask, add the solvent methanol wiring solution-forming, the methyl alcohol that adds is 3mL/g with intermediate volume mass ratio, take by weighing the methanol solution of NaOH again, wherein methyl alcohol is 7mL/g with the volume mass ratio of mineral alkali, NaOH and intermediate mol ratio are 1.2:1, at room temperature react 20h, suction filtration is removed the NaBr solid, filtrate is revolved to steam and is removed most of methyl alcohol, add the ether recrystallization and separate out unreacted solution NaOH and NaBr, revolve and steam final vacuum and be dried to constant weight and namely obtain the higher ionic liquid of purity (ionic liquid 5).Reach 95.83% through gas chromatographic analysis gained ionic liquid purity, productive rate reaches 95.12%.
Change by raw material can also make other hexanolactam class ionic liquids, and the present invention specifies it with regard to following a few class hexanolactam class ionic liquids and prepares application aspect the biofuel at the catalysis waste oil:
Ionic liquid 1 ionic liquid 2
Ionic liquid 3 ionic liquids 4
Ionic liquid 5 ionic liquids 6
Embodiment 4:
In the 100ml there-necked flask, add pre-treatment (owing to solid impurities such as moisture, starch, dust in the waste oil, to carry out pretreatment process such as filter just, dehydration, smart filter before use) waste oil 20.08g (its acid number is 13.09), put into the water-bath that has whipping appts, add 2.54 methyl alcohol and 0.49g ionic liquid (1), 40 ℃ of following heating reflux reaction 2h, reaction finish to transfer in the separating funnel leave standstill, layering, upper strata biofuel crude product and methyl alcohol, lower floor's glycerine and catalyzer.Subnatant reclaims catalyzer in-0.04MPa, 170 ℃ of following underpressure distillation, and methyl alcohol is reclaimed in the upper strata air distillation, makes biofuel and analyzes content through GC and reach 65.7%, and surveying its acid number is 1.83.
Embodiment 5:
Adding pretreated its acid number of waste oil 20.02g(in the 100ml there-necked flask is 14.23), put into the water-bath that has whipping appts, add 3.47 methyl alcohol and 0.89g ionic liquid (2), 60 ℃ of following heating reflux reaction 1h, reaction finish to transfer in the separating funnel leave standstill, layering, upper strata biofuel crude product and methyl alcohol, lower floor's glycerine and catalyzer.Subnatant reclaims catalyzer in-0.04MPa, 170 ℃ of following underpressure distillation, and methyl alcohol is reclaimed in the upper strata air distillation, makes biofuel and analyzes content through GC and reach 82.8%, and surveying its acid number is 1.32.
Embodiment 6:
Adding pretreated its acid number of waste oil 20.10g(in the 100ml there-necked flask is 23.85), put into the water-bath that has whipping appts, add 5.79 methyl alcohol and 0.89g ionic liquid (3), 80 ℃ of following heating reflux reaction 2h, reaction finish to transfer in the separating funnel leave standstill, layering, upper strata biofuel crude product and methyl alcohol, lower floor's glycerine and catalyzer.Subnatant reclaims catalyzer in-0.04MPa, 170 ℃ of following underpressure distillation, and methyl alcohol is reclaimed in the upper strata air distillation, makes biofuel and analyzes content through GC and reach 95.4%, and surveying its acid number is 0.48.
Embodiment 7:
Adding pretreated its acid number of waste oil 20.03g(in the 100ml there-necked flask is 23.85), put into the water-bath that has whipping appts, add 5.02 methyl alcohol and 1.03g ionic liquid (4), 70 ℃ of following heating reflux reaction 2h, reaction finish to transfer in the separating funnel leave standstill, layering, upper strata biofuel crude product and methyl alcohol, lower floor's glycerine and catalyzer.Subnatant reclaims catalyzer in-0.04MPa, 170 ℃ of following underpressure distillation, and methyl alcohol is reclaimed in the upper strata air distillation, makes biofuel and analyzes content through GC and reach 99.03%, surveys its acid number and is about 0.44.
Embodiment 8:
Adding pretreated its acid number of waste oil 20.12g(in the 100ml there-necked flask is 13.09), put into the water-bath that has whipping appts, add 7.63 primary isoamyl alcohol and 1.21g ionic liquid (5), 120 ℃ of following heating reflux reaction 5h, reaction finish to transfer in the separating funnel leave standstill, layering, upper strata biofuel crude product and primary isoamyl alcohol, lower floor's glycerine and catalyzer.Subnatant reclaims catalyzer in-0.04MPa, 170 ℃ of following underpressure distillation, and primary isoamyl alcohol is reclaimed in the upper strata air distillation, makes biofuel and analyzes content through GC and reach 97.89%, and surveying its acid number is 0.63.
Embodiment 9:
Adding pretreated its acid number of waste oil 20.06g(in the 100ml there-necked flask is 8.32), put into the water-bath that has whipping appts, add 4.89 Virahols and 1.13g ionic liquid (6), 85 ℃ of following heating reflux reaction 4h, reaction finish to transfer in the separating funnel leave standstill, layering, upper strata biofuel crude product and Virahol, lower floor's glycerine and catalyzer.Subnatant reclaims catalyzer in-0.04MPa, 170 ℃ of following underpressure distillation, and Virahols are reclaimed 90 ℃ of following air distillations in the upper strata, makes biofuel and analyzes content through GC and reach 97.41%, and surveying its acid number is 0.96.
Embodiment 10:
Adding pretreated its acid number of waste oil 19.98g(in the 100ml there-necked flask is 9.54), put into the water-bath that has whipping appts, add 4.08 ethanol and 1.14g ionic liquid (4), 80 ℃ of following heating reflux reaction 3h, reaction finish to transfer in the separating funnel leave standstill, layering, upper strata biofuel crude product and ethanol, lower floor's glycerine and catalyzer.Subnatant reclaims catalyzer in-0.04MPa, 170 ℃ of following underpressure distillation, and ethanol is reclaimed in the upper strata air distillation, makes biofuel and analyzes content through GC and reach 98.76%, and surveying its acid number is 0.41.
Embodiment 11:
Adding pretreated its acid number of waste oil 20.11g(in the 100ml there-necked flask is 8.32), put into the water-bath that has whipping appts, add 8.01 propyl carbinols and 1.98g ionic liquid (4), 100 ℃ of following heating reflux reaction 1h, reaction finish to transfer in the separating funnel leave standstill, layering, upper strata biofuel crude product and propyl carbinol, lower floor's glycerine and catalyzer.Subnatant reclaims catalyzer in-0.04MPa, 170 ℃ of following underpressure distillation, and propyl carbinol is reclaimed in the upper strata air distillation, makes biofuel and analyzes content through GC and reach 93.98%, and surveying its acid number is 0.89.
Embodiment 12:
In the 100ml there-necked flask, add pretreated waste oil 20.15g, put into the water-bath that has whipping appts, add 4.89 methyl alcohol and 1.21g ionic liquid (4), 70 ℃ of following heating reflux reaction 2h, reaction finish to transfer in the separating funnel leave standstill, layering, upper strata biofuel crude product and methyl alcohol, lower floor's glycerine and catalyzer.Methyl alcohol is reclaimed in the upper strata air distillation, considers the simple and convenient of cost recovery and experiment, and subnatant is directly used in follow-up revision test, investigates the reusability of catalyzer.Reuse 7 times (reaction conditions is the same) the content difference 99.01%, 98.87%, 98.92%, 98.26%, 98.13%, 98.01%, 97.54% of biofuel.Catalyst activity does not obviously reduce.
Embodiment 13:
Adding pretreated its acid number of waste oil 20.01g(in the 100ml there-necked flask is 23.72), put into the water-bath that has whipping appts, add the acid hexanolactam class of 5.02 methyl alcohol and 1.02g ionic liquid, 70 ℃ of following heating reflux reaction 2h, reaction finish to transfer in the separating funnel leave standstill, layering, upper strata biofuel crude product and methyl alcohol, lower floor's glycerine and catalyzer.Subnatant reclaims catalyzer in-0.04MPa, 170 ℃ of following underpressure distillation, and methyl alcohol is reclaimed in the upper strata air distillation, makes biofuel and analyzes content through GC and reach 89.03%, surveys its acid number and is about 1.12.
Claims (10)
1. hexanolactam class alkali ionic liquid, it is characterized in that: its general formula is:
Wherein n is the integer of 1-8, and R is H or C
1-C
12Alkyl.
2. a kind of hexanolactam class alkali ionic liquid according to claim 1 is characterized in that: n=1～5.
3. the preparation method of hexanolactam class alkali ionic liquid according to claim 1 and 2, it is characterized in that: step is as follows:
(1) hexanolactam class material and halogenated alkane in solvent at N
2Synthetic intermediate in the atmosphere, described intermediate is through ethyl acetate and its unreacted solution of ether flush away, and rotary evaporation obtains the higher intermediate of purity;
(2) again intermediate is dissolved in the methyl alcohol, obtains hexanolactam class ionic liquid with inorganic alkali alcosol prepared in reaction again.
4. the preparation method of hexanolactam class alkali ionic liquid according to claim 3, it is characterized in that: the described hexanolactam class of step (1) material comprises any one in hexanolactam, N-methyl caprolactam, N-ethyl hexanolactam, N-propyl group hexanolactam or the N-butyl hexanolactam.
5. the preparation method of hexanolactam class alkali ionic liquid according to claim 3, it is characterized in that: the described halogenated alkane of step (1) is C
1-C
8Bromo alkane, comprise a kind of in bromic ether, 1-bromo propane, bromination of n-butane or the 1-bromo pentane; Hexanolactam class material and haloalkane mol ratio are 1:0.5～2; Described solvent comprises a kind of in ethanol, acetonitrile or the toluene; Solvent quality is the 10%-50% of hexanolactam class material mass; Described synthetic intermediate temperature of reaction is 70～120 ℃, reaction 4～12h.
6. the preparation method of hexanolactam class alkali ionic liquid according to claim 3, it is characterized in that: the described hexanolactam class of step (1) material is hexanolactam; Described halohydrocarbon is bromination of n-butane; Described solvent is acetonitrile.
7. the preparation method of hexanolactam class alkali ionic liquid according to claim 3, it is characterized in that: the described intermediate of step (2) is dissolved in methyl alcohol, and methyl alcohol is 1～4ml/g with intermediate volume mass ratio;
Described mineral alkali comprises NaOH, KOH, NaHCO
3,, KHCO
3Or Ca (OH)
2A kind of or at least two kinds of mixtures wherein; Alcohol is methyl alcohol in the described inorganic alkali alcosol, and methyl alcohol is 5～8ml/g with mineral alkali volume mass ratio;
The reaction mol ratio of described mineral alkali and intermediate is 0.9～1.5:1, and at room temperature the reaction times is 12～28h.
8. the hexanolactam class alkali ionic liquid catalysis waste oil according to claim 1 and 2 application for preparing biofuel.
9. the hexanolactam class alkali ionic liquid catalysis waste oil according to claim 8 application for preparing biofuel, it is characterized in that: waste oil as catalyzer, prepares biofuel with alkyl alcohol by esterification and transesterification reaction with ionic liquid.
10. the hexanolactam class alkali ionic liquid catalysis waste oil according to claim 9 application for preparing biofuel is characterized in that: described waste oil comprises the wherein a kind of of acidifying oil, sewer oil, hogwash fat, swill oil; Ionic liquid is 2%～10% of waste oil quality; Described alkyl alcohol comprises the wherein a kind of or at least two kinds of mixtures in methyl alcohol, ethanol, Virahol, propyl carbinol, the primary isoamyl alcohol, and the alkyl alcohol consumption is 10%～40% of waste oil quality; Described esterification and transesterification reaction temperature are 40～120 ℃, and the reaction times is 1～5h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310190168.9A CN103265490B (en) | 2013-05-21 | 2013-05-21 | A kind of Caprolactam basic ionic liquid and preparation method thereof and application |
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| CN104629868A (en) * | 2015-02-02 | 2015-05-20 | 中国石油大学(华东) | Preparation method of low-sulfur diesel oil antiwear agent |
| CN105536866A (en) * | 2015-12-11 | 2016-05-04 | 中国石油大学(北京) | Ionic-like liquid and preparation method and application thereof in preparation of alkylated oil |
| CN109337027A (en) * | 2018-09-19 | 2019-02-15 | 常州大学 | A method of using Caprolactam basic ionic liquid as catalyst preparation phenolic resin |
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| CN105536866A (en) * | 2015-12-11 | 2016-05-04 | 中国石油大学(北京) | Ionic-like liquid and preparation method and application thereof in preparation of alkylated oil |
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