CN103521263A - Morpholine salt ionic liquid catalyst and preparation method and application thereof - Google Patents
Morpholine salt ionic liquid catalyst and preparation method and application thereof Download PDFInfo
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- Y02E50/10—Biofuels, e.g. bio-diesel
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Abstract
The invention relates to a morpholine salt ionic liquid catalyst and a preparation method thereof as well as a method for preparing biodiesel by use of morpholine salt ionic liquid catalyzing waste oil. The catalyst provided by the invention is of the general formula (I) and is prepared by the following steps of synthesizing an intermediate through a reaction between N-methylmorpholine and halogenated alkane; synthesizing morpholine salt through a reaction between morpholine and an alcoholic solution of inorganic base or salt; preparing the morpholine salt ionic liquid catalyst through a reaction between the intermediate and the morpholine salt. The ionic liquid is prepared by a two-step process, and the raw materials are cheap. The biodiesel is prepared by taking the waste oil and alkyl alcohol as raw materials and the morpholine salt ionic liquid as a catalyst; after the reaction, the ionic liquid and the product are subjected to automatic phase splitting. By adopting the catalyst provided by the invention to prepare biodiesel, the activity of the catalyst is high, and the dosage is small; the preparation conditions of the catalyst are mild, the toxicity is low, and the catalyst is easy to degrade; the reaction conditions are mild, and the reaction time is short; moreover, the reaction process is simple, the product is easy to separate, pollution is avoided, and the yield is high.
Description
Technical field
The present invention relates to a kind of morpholine class ionic-liquid catalyst, its preparation method and take that it prepares purposes and the method for biodiesel as catalyst waste oil and alkylol, belong to ionic liquid-catalyzed technical field.
Background technology
Along with expanding economy, the mankind are more and more higher to the requirement of the energy and quality of life, also the problems such as energy shortage and environmental pollution have been brought simultaneously, in recent years along with the trend of worldwide diesel oil of vehicle is day by day accelerated, and the resource of petrifaction diesel is limited, so the mankind have started to turn to the research direction of reproducible biodiesel.Biodiesel, claim again fuel methyl esters, that triglycerides to extract in vegeto-animal fat reacts under certain catalyst action with methyl alcohol or ethanol, utilize the glyceryl on methoxy substitution LCFA, glyceryl is fragmented into three LCFA methyl esters, thereby shorten carbon chain lengths, reduce the viscosity of oil plant, improve mobile performance and gasification and the combustibility of oil plant, reach the standard of commercial fuel.
Ionic liquid is also referred to as room temperature fuse salt, refers to that fusing point is below 100 ℃ and the salt compounds being in a liquid state at ambient temperature, be comprised of zwitterion completely.Because it has steam, forced down in recent years, not volatile, toxicity is little, be easy to the advantages such as recovery by extensive concern.The liquid temperature scope of ionic liquid is wide, and fusing point is low, and chemical stability is good, of a great variety and can design, conductance is high, and electrochemical window is wide, can dissolve most of organic matters and inorganic matter, chemical reaction is carried out smoothly in homogeneous phase, greatly reduce the volume of reactor.In electrochemistry, plating, organic, analysis, catalysis, the field such as lubricated, there is its application at present.Utilize it catalysis to prepare biological produce oil.
US2009270248 discloses a kind of novel alkali ionic liquid [Cat
+-Z-Bas] [X
-], Cat wherein
+=cationic moiety, Bas=basic moiety, Z=connects Cat
+covalent bond with Bas; Or 1,2 or 3 aliphatic divalent linkers, described in each, aliphatic divalent linker all comprises 1 to 10 carbon atom and optionally comprises 1, two or 3 oxygen atoms; X
-=anionicsite, and condition is that Bas is not-OH.Its basic moiety is showed by cation, the catalysis that is designed to adapt to chemical process in the most effective mode according to reaction environment is with separated, than conventional dicyandiamide solution, the ionic liquid of this invention has low vapour pressure, adjustable polarity and performance and high heat endurance.And the reaction with alkyl halide and excessive diazabicyclo [2,2,2] octane obtains the ionic liquid of alkaline series.
WO2012121447A1 discloses a kind of compound ion liquid, and as catalyst, carries out the method for esterification, acetylization reaction synthesis of acetyl tri-n-butyl citrate, and the structure of its compound ion liquid is as follows:
Wherein X represents HSO
4 -, H
2pO
4 -, CH
3sO
3 -, BF
4 -.This compound ion liquid have than the stronger acidity of inorganic acid and miscible with raw material, synthesis technique is simple, conversion ratio is high, esterification is selectively greater than 99%, yield reaches more than 98%, and accessory substance is few, without advantages such as decolorization filterings.And catalyst is reusable, in carrying out follow-up acetylization reaction, reaction temperature is low, with short production cycle, equipment investment is few, energy consumption is little, cost is low.
CN101856512 discloses the technology that a kind of basic imidazole class alkali ionic liquid catalysis food and beverage waste oil and grease is prepared biodiesel, and the molecular formula of alkaline ionic liquid catalyst is:
This invention is mainly after waste oil is dewatered, under the existence that is catalyst at alkali ionic liquid, carry out esterification with methyl alcohol, product is through Distillation recovery methyl alcohol, saturated sodium-chloride is washed after thick ester by hot water wash to neutral, finally adds deicer to obtain refined biometric diesel oil.This technological operation is simple, and reaction condition is gentle, but this process costs is higher, and the industrial value of imidazoles is higher.
CN102120728A discloses a kind of with the ionic liquid-catalyzed method of preparing polyoxymethylene dimethyl ether of caprolactam class.Its general structure is as follows,
Wherein m represents 0 to 8 integer, and we select m=0,3 or 4 conventionally; X-is bisulfate ion, dihydrogen phosphate, p-methyl benzenesulfonic acid root, trifluoromethayl sulfonic acid root, a kind of in pyrovinic acid root, trifluoroacetic acid root, formate, acetate.By regulating the kind of anion, the ionic liquid of preparation different acidity, and synthetic ionic liquid easily degrades compared to imidazoles, pyridines ionic liquid, and environment is more added with, and reusability is strong.
CN103031217A discloses a kind of method of pyrrolidinone compounds alkali ionic liquid catalysis Preparation of Biodiesel from Waste Oils.Its general structure is:
Wherein n represents 1～8 integer, and R is the alkyl of H or C1～C12, and ethoxy or vinyl are selected n=1,2,3,4 or 5 alkyl substituent conventionally.Under the condition of this ionic liquid, having overcome classical inverse should be in shortcomings such as catalyst are serious to equipment corrosion, reaction rate is slow, the time is long, energy consumption is large, yield is low, and the activity of catalyst is higher, course of reaction is simple, product separation is easy, the advantage such as pollution-free.
The problems such as in prior art, traditional catalyst exists, product difficult separation serious to equipment corrosion, energy consumption is large, yield is low.And be applied to biodiesel ionic-liquid catalyst be mainly acidic ion liquid at present, the cost of material of its production is higher.
Summary of the invention
One of object of the present invention is to provide a kind of morpholine salt ionic liquid with double-function catalyzing activity, and one of object is also to provide the research method of one-step catalytic Preparation of Biodiesel from Waste Oils.It is raw material that the present invention adopts waste oil and alkylol, and selecting morpholine salt ionic liquid is catalyst, has both reduced production cost, can make again reaction carry out in homogeneous reaction, and reaction condition is gentle.
For reaching above object, the present invention has adopted following technical scheme:
A salt ionic-liquid catalyst, it is the compound of general formula (I):
Wherein, R is alkyl.
Preferably, R is-CH
2cH
3,-CH
2cH
2cH
3,-CH
2cH
2cH
2cH
3,-CH
2cH
2cH
2cH
2cH
3or-CH
2cH
2cH
2cH
2cH
2cH
3in a kind of.
One of object of the present invention is also to provide the preparation method of described morpholine salt ionic-liquid catalyst, comprises the steps:
(1) N-methylmorpholine reacts synthetic intermediate in solvent with halogenated alkane;
(2) use morpholine to react synthesize morpholine salt with the alcoholic solution of inorganic base or salt;
(3) intermediate of step (1) gained reacts and obtains morpholine salt ionic-liquid catalyst with the alkylbenzyldimethylasaltsum saltsum of step (2) gained in solvent.
Halogenated alkane wherein can be chloralkane, brominated alkanes, alkane iodide or fluoric ether; As optimal technical scheme, preparation method of the present invention, the brominated alkanes that halogenated alkane described in step (1) is C1～C8, be preferably the one kind or two or more mixture in bromic ether, 1-bromo propane, 1-bromination of n-butane, 1-bromo pentane, bromo n-hexane, more preferably bromination of n-butane.
Preferably, described solvent is the one kind or two or more mixture in methyl alcohol, ethanol, acetonitrile, toluene, and productive rate and purity under the same conditions, is preferably acetonitrile after deliberation.
Preferably, described N-methylmorpholine and the mol ratio of halogenated alkane are 1:0.5～2, consider the partial loss in course of reaction, and the amount of 1-bromination of n-butane should be slightly higher than theoretical value, is preferably 1:1～2, more preferably 1:1.1.
Preferably, the quality of described solvent is 20%～50% of N-methylmorpholine quality, such as being 22%, 25%, 29%, 33%, 38%, 41%, 44%, 47%, 49% etc., is preferably 20%～40%.The amount of solvent affects the carrying out of reaction very little, and along with the concentration of carrying out of reaction becomes large, impact is stirred, and is excessively unfavorable for post processing, has also increased reaction cost simultaneously.Therefore, the amount of selective solvent of the present invention is 20%～50% of N-methylmorpholine quality.
Preferably, described in step (1), the temperature of reaction is 60～120 ℃, such as being 63 ℃, 66 ℃, 71 ℃, 75 ℃, 79 ℃, 84 ℃, 88 ℃, 92 ℃, 99 ℃, 104 ℃, 107 ℃, 110 ℃, 114 ℃, 119 ℃ etc., preferably 60～100 ℃, more preferably 70～90 ℃;
Preferably, the time of described reaction is 5～15h, such as being 5.5h, 6.1h, 6.5h, 7.0h, 7.5h, 9.0h, 9.5h, 11h, 13h, 14.5h etc., is preferably 6～10h, more preferably 6～8h;
Preferably, described reaction is at N
2in environment, carry out.Select N
2environment synthetic intermediate, can improve productive rate and the purity of product.
As optimal technical scheme, preparation method of the present invention, the inorganic base described in step (2) or salt are NaOH, KOH, NaHCO
3, KHCO
3in one kind or two or more mixture, be preferably NaOH and/or KOH, more preferably KOH.
Preferably, described alcoholic solution is the one kind or two or more mixture in methyl alcohol, ethanol, isopropyl alcohol, n-butanol, is preferably methyl alcohol and/or ethanol, more preferably methyl alcohol.
Preferably, the mol ratio of described morpholine and inorganic base or salt is 1:0.5～2, such as being 1:0.6,1:0.8,1:1.1,1:1.3,1:1.5,1:1.7,1:1.9 etc., is preferably 1:1.
Preferably, the temperature of described reaction is 40～100 ℃, for example, be 42 ℃, 46 ℃, 49 ℃, 53 ℃, 58 ℃, 63 ℃, 66 ℃, 71 ℃, 75 ℃, 79 ℃, 84 ℃, 88 ℃, 92 ℃, 99 ℃, preferably 50～90 ℃, and more preferably 60～80 ℃.
Preferably, the time of described reaction is 0.5h～5h, such as being 0.7h, 0.9h, 1.2h, 1.7h, 2.1h, 2.5h, 2.9h, 3.5h, 4.0h, 4.5h, 4.9h etc., and preferred 0.5h～3h, more preferably 1h～2h.
As optimal technical scheme, preparation method of the present invention, the solvent described in step (3) is the one kind or two or more mixture in methyl alcohol, ethanol, carrene or ether.
Preferably, the amount of described solvent is 1～20ml/g with the ratio of intermediate, is the solvent that every gram of intermediate is used 1～20ml, such as being 3ml/g, 6ml/g, 9ml/g, 12ml/g, 16ml/g, 19ml/g etc., be preferably 3～15ml/g, more preferably 5～8ml/g.
Preferably, the mol ratio of described intermediate and alkylbenzyldimethylasaltsum saltsum is 0.9～1.2:1, such as being 0.95:1,1.0:1,1.05:1,1.1:1,1.15:1 etc.
Preferably, the time of described reaction is 12～24h, such as being 14h, 16h, 18h, 20h, 23h etc., is preferably 12～15h.
One of object of the present invention is also to provide the purposes of described morpholine salt ionic-liquid catalyst in catalysis Preparation of Biodiesel from Waste Oils.
The method of purposes of the present invention is, it is catalyst that waste oil be take morpholine salt ionic liquid of the present invention, prepares biodiesel with alkylol by esterification and ester exchange reaction.
As optimal technical scheme, the method for described purposes, described waste oil be waste oil, acidification oil, hogwash fat in one kind or two or more mixture;
Preferably, the quality of described ionic liquid is 1%～10% of waste oil quality, such as being 2%, 4%, 6%, 9% etc., and preferably 1%～7%;
Preferably, described alkylol be methyl alcohol, ethanol, isopropyl alcohol, n-butanol in one kind or two or more mixture;
Preferably, the quality of described alkylol is 10%～60% of waste oil quality, such as being 12%, 15%, 20%, 25%, 30%, 34%, 39%, 43%, 48%, 52%, 55%, 59% etc., and preferably 10%～40%;
Preferably, described esterification and the temperature of ester exchange reaction are 40～90 ℃, such as being 42 ℃, 46 ℃, 49 ℃, 53 ℃, 58 ℃, 63 ℃, 66 ℃, 71 ℃, 75 ℃, 79 ℃, 84 ℃, 88 ℃ etc., and preferably 40～80 ℃;
Preferably, the time of described reaction is 1～4h, such as being 1.2h, 1.7h, 2.1h, 2.5h, 2.9h, 3.5h, 3.8h etc., preferably 1～3h.
The present invention has following beneficial effect:
1, selected ionic liquid synthesis condition is gentle, and reaction is simple, and it is low that cost of material is studied more glyoxaline ion liquid more at present, for realizing industrialization, provides advantage.
2, selected ionic liquid catalyst activity is high, consumption is few, toxicity is low.
3, high, the reaction of preparation biodiesel raw materials used utilization rate is carried out in homogeneous reaction, the automatic phase-splitting of reaction afterproduct.
4, selected ionic liquid temperature range is wide, alkalescence is strong, course of reaction is easy to control, and catalyst reusability is strong.
5, in preparation biodiesel product pollution-free, can not bring the problems such as corrosion to equipment, production process environmental protection, reduced production cost.
The specific embodiment
Below by the specific embodiment, further illustrate technical scheme of the present invention.
Described alkali ion liquid catalyst is:
The preparation method of ionic liquid 1 is as follows:
(1) N
2in environment, N-methylmorpholine reacts 12h synthetic intermediate with bromic ether with the mol ratio of 1:1.1 in acetonitrile at 70 ℃, and wherein the quality of acetonitrile is 20% of N-methylmorpholine quality;
(2) methanol solution that uses morpholine and KOH reacts 0.5h synthesize morpholine salt in 60 ℃, and wherein the mol ratio of morpholine and KOH is 1:1;
(3) intermediate of step (1) gained reacts 24h with the alkylbenzyldimethylasaltsum saltsum of step (2) gained with the mol ratio of 1:1 and obtains morpholine salt ionic-liquid catalyst 1 in carrene under room temperature, and wherein the amount of solvent is 5ml/g with the ratio of intermediate.
The preparation method of ionic liquid 2 is as follows:
(1) N
2in environment, N-methylmorpholine reacts 12h synthetic intermediate with 1-bromo propane with the mol ratio of 1:0.8 in methyl alcohol at 70 ℃, and wherein the quality of methyl alcohol is 35% of N-methylmorpholine quality;
(2) ethanolic solution that uses morpholine and NaOH reacts 0.5h synthesize morpholine salt in 60 ℃, and wherein the mol ratio of morpholine and NaOH is 1:0.5;
(3) intermediate of step (1) gained reacts 24h with the alkylbenzyldimethylasaltsum saltsum of step (2) gained with the mol ratio of 0.9:1 and obtains morpholine salt ionic-liquid catalyst 2 in methyl alcohol under room temperature, and wherein the amount of solvent is 20ml/g with the ratio of intermediate.
The preparation method of ionic liquid 3 is as follows:
(1) N-methylmorpholine reacts 12h synthetic intermediate with 1-iodo-n-butane with the mol ratio of 1:1.5 in ethanol at 70 ℃, and wherein the quality of ethanol is 30% of N-methylmorpholine quality;
(2) alcoholic solution that uses morpholine and NaOH and KOH reacts 0.5h synthesize morpholine salt in 60 ℃, and wherein the mol ratio of morpholine and NaOH and KOH is 1:2;
(3) intermediate of step (1) gained reacts 24h with the alkylbenzyldimethylasaltsum saltsum of step (2) gained with the mol ratio of 1.2:1 and obtains morpholine salt ionic-liquid catalyst 3 in ethanol under room temperature, and wherein the amount of solvent is 1ml/g with the ratio of intermediate.
The preparation method of ionic liquid 4 is as follows:
(1) N
2in environment, N-methylmorpholine and 1-chloro-n-pentane react 0.5h synthetic intermediate in 60 ℃ with the mol ratio of 1:0.5 in toluene, and wherein the quality of toluene is 40% of N-methylmorpholine quality;
(2) use morpholine and KHCO
3alcoholic solution in 60 ℃ of reaction 0.5h synthesize morpholine salt, wherein morpholine and KHCO
3mol ratio be 1:1.5;
(3) intermediate of step (1) gained reacts 24h with the alkylbenzyldimethylasaltsum saltsum of step (2) gained with the mol ratio of 1.1:1 and obtains morpholine salt ionic-liquid catalyst 4 in ether under room temperature, and wherein the amount of solvent is 10ml/g with the ratio of intermediate.
The preparation method of ionic liquid 5 is as follows:
(1) N
2in environment, N-methylmorpholine and 1-bromo n-hexane react 0.5h synthetic intermediate in 60 ℃ with the mol ratio of 1:2 in acetonitrile, and wherein the quality of acetonitrile is 50% of N-methylmorpholine quality;
(2) use morpholine and NaHCO
3alcoholic solution in 60 ℃ of reaction 0.5h synthesize morpholine salt, wherein morpholine and NaHCO
3mol ratio be 1:1.7;
(3) intermediate of step (1) gained reacts 24h with the alkylbenzyldimethylasaltsum saltsum of step (2) gained with the mol ratio of 1:1 and obtains morpholine salt ionic-liquid catalyst 5 in the mixed solvent of methyl alcohol and ether under room temperature, and wherein the amount of solvent is 15ml/g with the ratio of intermediate.
Embodiment utilizes the above-mentioned ionic liquid 1-5 making to prepare the embodiment of biodiesel below.
Embodiment 1:
In 100ml there-necked flask, add pretreated waste oil 20.13g (its acid number is 13.12), put into the water-bath with agitating device, insert thermometer and condenser pipe, open condensed water, heated water bath temperature reaches 40 ℃, adds 2.18 methyl alcohol and 0.21g ionic liquid (1), heating reflux reaction 2h at 40 ℃, reaction finishes to transfer to standing in separatory funnel, layering, upper strata biodiesel crude product and methyl alcohol, lower floor's glycerine and catalyst.Catalyst is reclaimed in subnatant decompression distillation at-0.04MPa, 170 ℃, and methyl alcohol is reclaimed in upper strata air-distillation at 70 ℃, makes biodiesel and through GC, analyzes content and reach 83.56%, and surveying its acid number is 0.87.
Embodiment 2:
In 100ml there-necked flask, add pretreated waste oil 21.33g (its acid number is 11.96), put into the water-bath with agitating device, insert thermometer and condenser pipe, open condensed water, heated water bath temperature reaches 50 ℃, adds 5.33g methyl alcohol and 0.43g ionic liquid (2), heating reflux reaction 2h at 50 ℃, reaction finishes to transfer to standing in separatory funnel, layering, upper strata biodiesel crude product and methyl alcohol, lower floor's glycerine and catalyst.Catalyst is reclaimed in subnatant decompression distillation at-0.04MPa, 170 ℃, and methyl alcohol is reclaimed in upper strata air-distillation at 70 ℃, makes biodiesel and through GC, analyzes content and reach 87.57%, and surveying its acid number is 0.63.
Embodiment 3:
In 100ml there-necked flask, add pretreated waste oil 21.57g (its acid number is 12.26), put into the water-bath with agitating device, insert thermometer and condenser pipe, open condensed water, heated water bath temperature reaches 60 ℃, adds 6.47g methyl alcohol and 0.87g ionic liquid (3), heating reflux reaction 2h at 60 ℃, reaction finishes to transfer to standing in separatory funnel, layering, upper strata biodiesel crude product and methyl alcohol, lower floor's glycerine and catalyst.Catalyst is reclaimed in subnatant decompression distillation at-0.04MPa, 170 ℃, and methyl alcohol is reclaimed in upper strata air-distillation at 70 ℃, makes biodiesel and through GC, analyzes content and reach 97.16%, and surveying its acid number is 0.28.
Embodiment 4:
In 100ml there-necked flask, add pretreated waste oil 20.63g (its acid number is 11.46), put into the water-bath with agitating device, insert thermometer and condenser pipe, open condensed water, heated water bath temperature reaches 70 ℃, adds 7.28g methyl alcohol and 1.02g ionic liquid (4), heating reflux reaction 2h at 70 ℃, reaction finishes to transfer to standing in separatory funnel, layering, upper strata biodiesel crude product and methyl alcohol, lower floor's glycerine and catalyst.Catalyst is reclaimed in subnatant decompression distillation at-0.04MPa, 170 ℃, and methyl alcohol is reclaimed in upper strata air-distillation at 70 ℃, makes biodiesel and through GC, analyzes content and reach 96.87%, and surveying its acid number is 0.31.
Embodiment 5:
In 100ml there-necked flask, add pretreated waste oil 20.56g (its acid number is 12.42), put into the water-bath with agitating device, insert thermometer and condenser pipe, open condensed water, heated water bath temperature reaches 80 ℃, adds 8.24g methyl alcohol and 1.25g ionic liquid (5), heating reflux reaction 2h at 80 ℃, reaction finishes to transfer to standing in separatory funnel, layering, upper strata biodiesel crude product and methyl alcohol, lower floor's glycerine and catalyst.Catalyst is reclaimed in subnatant decompression distillation at-0.04MPa, 170 ℃, and methyl alcohol is reclaimed in upper strata air-distillation at 70 ℃, makes biodiesel and through GC, analyzes content and reach 93.21%, and surveying its acid number is 0.58.
Embodiment 6:
In 100ml there-necked flask, add pretreated waste oil 20.53g (its acid number is 12.35), put into the water-bath with agitating device, insert thermometer and condenser pipe, open condensed water, heated water bath temperature reaches 70 ℃, adds 6.17g methyl alcohol and 0.83g ionic liquid (3), heating reflux reaction 2h at 70 ℃, reaction finishes to transfer to standing in separatory funnel, layering, upper strata biodiesel crude product and methyl alcohol, lower floor's glycerine and catalyst.Catalyst is reclaimed in subnatant decompression distillation at-0.04MPa, 170 ℃, and methyl alcohol is reclaimed in upper strata air-distillation at 70 ℃, makes biodiesel and through GC, analyzes content and reach 96.88%, and surveying its acid number is 0.31.
Applicant's statement, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to the selection of the interpolation of the equivalence replacement of each raw material of product of the present invention and auxiliary element, concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (10)
1. a morpholine salt ionic-liquid catalyst, it is the compound of general formula (I):
Wherein, R is alkyl.
2. catalyst according to claim 1, is characterized in that, R is-CH
2cH
3,-CH
2cH
2cH
3,-CH
2cH
2cH
2cH
3,-CH
2cH
2cH
2cH
2cH
3or-CH
2cH
2cH
2cH
2cH
2cH
3in a kind of.
3. a preparation method for the morpholine salt ionic-liquid catalyst described in claim 1 or 2, comprises the steps:
(1) N-methylmorpholine reacts synthetic intermediate in solvent with halogenated alkane;
(2) use morpholine to react synthesize morpholine salt with the alcoholic solution of inorganic base or salt;
(3) intermediate of step (1) gained reacts and obtains morpholine salt ionic-liquid catalyst with the alkylbenzyldimethylasaltsum saltsum of step (2) gained in solvent.
4. preparation method according to claim 3, it is characterized in that, the brominated alkanes that halogenated alkane described in step (1) is C1～C8, be preferably the one kind or two or more mixture in bromic ether, 1-bromo propane, 1-bromination of n-butane, 1-bromo pentane, 1-bromo n-hexane, more preferably bromination of n-butane;
Preferably, described solvent is the one kind or two or more mixture in methyl alcohol, ethanol, acetonitrile, toluene, is preferably acetonitrile;
Preferably, described N-methylmorpholine and the mol ratio of halogenated alkane are 1:0.5～2, are preferably 1:1～2, more preferably 1:1.1;
Preferably, the quality of described solvent is 20%～50% of N-methylmorpholine quality, is preferably 20%～40%.
According to described in claim 3 or 4 preparation method, it is characterized in that, described in step (1) reaction temperature be 60～120 ℃, preferably 60～100 ℃, more preferably 70～90 ℃;
Preferably, the time of described reaction is 5～15h, is preferably 6～10h, more preferably 6～8h;
Preferably, described reaction is at N
2in environment, carry out.
According to described in claim 3-5 any one preparation method, it is characterized in that, the inorganic base described in step (2) or salt are NaOH, KOH, NaHCO
3, KHCO
3in one kind or two or more mixture, be preferably NaOH and/or KOH, more preferably KOH;
Preferably, described alcoholic solution is the one kind or two or more mixture in methyl alcohol, ethanol, isopropyl alcohol, n-butanol, is preferably methyl alcohol and/or ethanol, more preferably methyl alcohol;
Preferably, the mol ratio of described morpholine and inorganic base or salt is 1:0.5～2, is preferably 1:1;
Preferably, the temperature of described reaction is 40～100 ℃, preferably 50～90 ℃, and more preferably 60～80 ℃;
Preferably, the time of described reaction is 0.5h～5h, preferably 0.5h～3h, more preferably 1h～2h.
According to described in claim 3-6 any one preparation method, it is characterized in that, the solvent described in step (3) is the one kind or two or more mixture in methyl alcohol, ethanol, carrene or ether;
Preferably, the amount of described solvent is 1～20ml/g with the ratio of intermediate, is preferably 3～15ml/g, more preferably 5～8ml/g;
Preferably, the mol ratio of described intermediate and alkylbenzyldimethylasaltsum saltsum is 0.9～1.2:1;
Preferably, the time of described reaction is 12～24h, is preferably 12～15h.
8. the purposes of morpholine salt ionic-liquid catalyst described in claim 1-7 any one, is characterized in that, described morpholine salt ionic-liquid catalyst is for catalysis Preparation of Biodiesel from Waste Oils.
9. the method for purposes described in claim 8, is characterized in that, it is catalyst that waste oil be take morpholine salt ionic liquid described in claim 1-7 any one, prepares biodiesel with alkylol by esterification and ester exchange reaction.
10. method according to claim 9, is characterized in that, described waste oil be waste oil, acidification oil, hogwash fat in one kind or two or more mixture;
Preferably, the quality of described ionic liquid is 1%～10% of waste oil quality, preferably 1%～7%;
Preferably, described alkylol be methyl alcohol, ethanol, isopropyl alcohol, n-butanol in one kind or two or more mixture;
Preferably, the quality of described alkylol is 10%～60% of waste oil quality, preferably 10%～40%;
Preferably, described esterification and the temperature of ester exchange reaction are 40～90 ℃, preferably 40～80 ℃;
Preferably, the time of described reaction is 1～4h, preferably 1～3h.
Priority Applications (1)
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| CN109593170A (en) * | 2018-11-29 | 2019-04-09 | 常州大学 | Using morpholine anionic species alkali ionic liquid as the method for catalyst preparation phenolic resin |
| CN111018710A (en) * | 2019-12-09 | 2020-04-17 | 沈阳化工大学 | Preparation method of dimethyl carbonate |
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| CN113813768A (en) * | 2021-09-29 | 2021-12-21 | 青岛科技大学 | Morpholine alkaline ionic liquid, and preparation method and application thereof |
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