CN103301857B - Preparation method of ternary compound solid base catalyst and method for catalyzed synthesis of novel biodiesel thereof - Google Patents
Preparation method of ternary compound solid base catalyst and method for catalyzed synthesis of novel biodiesel thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of a ternary compound solid base catalyst and a method for catalyzed synthesis of novel biodiesel thereof, and relates to the preparation method of the solid base catalyst and a method for catalyzed synthesis of novel biodiesel thereof. The invention aims to solve the problem that a phase homogenizing base catalyst adopted for preparing novel biodiesel at present is not high in reaction activity and complex in post-treatment process, the reactants are neutralized and washed to lead to discharge of a mass of wastewater, and the environment is polluted. The preparation method comprises the following steps: 1, preparing an x-KF/MO-MMT precursor; and 2, drying and roasting to obtain the catalyst. The method for catalyzed synthesis of novel biodiesel comprises the following steps: adding the reaction raw materials and the catalyst to a reactor with a return condensing device; stirring to react under protection of nitrogen at normal pressure; and then, performing centrifugal separation and decompressing and distillation to obtain the biodiesel. The ternary compound solid base catalyst prepared by the method provided by the invention can be used as a catalyst for synthesizing novel biodiesel.
Description
Technical field
The present invention relates to a kind of preparation method of solid base catalyst and utilize it to catalyze and synthesize the method for novel biodiesel.
Background technology
Character and the petrifaction diesel of biodiesel are close, are a kind of environmental protection and reproducible liquid fuel, are the petrifaction diesel substitute of high-quality.Biodiesel refers to the aliphatic acid mono alkyl ester obtained through ester exchange reaction with short chain alcohol (methyl alcohol or ethanol) by animal and plant fat (fatty acid triglycercide).
Formula 1 biodiesel ester exchange reaction equation
R in above formula
1, R
2, R
3for C
12 ~ 24the straight-chain alkyl of (saturated or unsaturated), ROH represents lower aliphatic alcohols, and many employing methyl alcohol and ethanol, wherein glyceride mostly is mixed glyceride (i.e. R
1≠ R
2or ≠ R
3).Biodiesel its have the features such as biodegradable, renewable, environmental friendliness, but only containing an ester group in its molecular structure, oxygen content is lower, and combustion and emission performance is not ideal enough.Therefore, to the further modification of biodiesel, the development for development China's grease and related industries is all very important.
Novel biodiesel refers to introduces ether and the higher fuel of the oxygen content that generates by ester exchange reaction on the basis of biodiesel (fatty acid methyl ester).
Formula 2 novel biodiesel ester exchange reaction equation
Novel biodiesel ester (n=1,2,3,4,5,7,9,10,15,20) in above formula is compared with traditional biodiesel and fatty acid methyl ester (FAME), novel biodiesel has the viscosity calorific capacity close with petrifaction diesel, have lower density and higher Cetane number, sulfur content is low, pour point is low and the advantage such as the oxidation stability suitable with diesel oil.Meanwhile, novel biodiesel is due to the introducing of ether, and oxygen content increases, and burn more complete, that effectively can reduce restriction (comprises CO with unrestriced pollutant emission
2, SO
x, NO
x), can also discharge quantity of particulate matter be reduced.Because novel biodiesel has many-sided advantage than biodiesel, therefore, the research of novel biodiesel will receive increasing concern.
The people such as Jiang (Journal of Biomedicine and Biotechnology, 2011,2011,1 ~ 8) refining rapeseed oil is adopted, glycol monoethyl ether is raw material, and KOH is catalyst, and ester exchange reaction has prepared novel biodiesel rapeseed oil monoesters.Before reaction starts, first with ethanol pretreatment rapeseed oil removing aliphatic acid at 90 DEG C, vacuum is purified and is removed ethanol.Infrared detection, determines aliphatic acid, and ethanol removes completely.600mL refines rapeseed oil, 250mL glycol monoethyl ether, 0.6%KOH catalyst, 65 DEG C of reactions.After reacting completely, the rare HCl of thick product neutralizes, and be separated removing aqueous phase, vacuum is purified, removing glycol monoethyl ether, CaCl
2drying, obtains novel biodiesel rapeseed oil monoesters.
The refining cottonseed oil of the people such as Lee (contemporary chemical industry, 2012,41 (2): 116 ~ 119) employing and diethylene glycol monomethyl ether carry out ester exchange reaction and have prepared novel biodiesel cottonseed oil diethylene glycol dimethyl ether ester.Building-up process: cottonseed oil methyl esters is put in people's there-necked flask, add a certain amount of diethylene glycol dimethyl ether and a certain amount of solid KOH powder, open electric jacket and agitator, constantly distill out Methanol product in course of reaction and ensure that reaction continues forward and carries out, when in condenser pipe, no liquid oozes, mark reaction terminates.Move in separatory funnel after cooling, add in dilute hydrochloric acid solution and removing KOH, then with saturated NaCl aqueous solution washing 2 ~ 3 times, decompression distillation removes unnecessary diethylene glycol dimethyl ether and water, and end product is cottonseed oil diethylene glycol dimethyl ether ester.
The people such as Jiang (African Journal of Biotechnology, 2011,10 (72): 16300 ~ 16313) adopt refined palm oil and glycol monoethyl ether to be raw material, KOH is catalyst, and ester exchange reaction has prepared palm oil glycol monoethyl ether ester.Before reaction, first with ethanol pretreatment palm oil removing aliphatic acid at 90 DEG C, vacuum is purified and is removed ethanol.Infrared detection, determines free fatty, and ethanol removes completely.600mL refined palm oil, 210mL glycol monoethyl ether, 0.6%KOH catalyst, 80 DEG C of reactions.After reacting completely, the rare HCl of thick product neutralizes, and be separated removing aqueous phase, vacuum is purified, removing glycol monoethyl ether, CaCl
2drying, obtain novel biodiesel palm oil monoesters, productive rate can reach 85%.
The people such as Li (International Journal of Green Energy, 2012,9 (4): 376 ~ 387) adopt refining cottonseed oil and glycol monoethyl ether to carry out ester exchange reaction and prepare novel diesel cottonseed oil glycol monoethyl ether ester.By a certain amount of refining cottonseed oil and glycol monoethyl ether (, alcohol oil rate 8: 1), 1% (percent by volume) KOH adds in flask, 90 DEG C of reaction 2h.Rear rare HCl neutralization, decompression distillation and steam distillation remove unreacted cottonseed oil and glycol monoethyl ether completely respectively, finally use the dehydration of 4A type molecular sieve drying, obtain novel diesel cottonseed oil glycol monoethyl ether ester.
The people such as Jiang (regenerative resource, 2007,25 (1): 32 ~ 35) adopt refining rapeseed oil and glycol monoethyl ether to be raw material, prepare a kind of novel biodiesel, rapeseed oil glycol methyl ether ester.Join in the there-necked flask of 1000mL after a certain amount of rapeseed oil depickling is dewatered, when temperature in container be 60 DEG C constant time, add the potassium alkoxide solution prepared, after abundant reaction, solution in flask is transferred in separatory funnel, adds appropriate hydrochloric acid and make solution be neutral.Leave standstill 12h, layering, after the crude glycerine of removing separatory funnel lower floor yellowish-brown thickness, just obtain coarse biodiesel.By decompression distillation except glycol monoethyl ether excessive in dereaction, the soap salt that suction filtration produces except dereaction, then through washing is with dry repeatedly, obtain end product rapeseed oil glycol methyl ether ester, productive rate can reach 84%.
Above document is all be catalyst with KOH, and feedstock oil needs the pretreatment such as depickling dewaters, after reacting completely, product need move in separatory funnel and add in dilute hydrochloric acid solution and removing KOH, saturated NaCl solution washing, the post processings such as decompression distillation, end product is novel biodiesel.
Open and wait people's (oil and foodstuffs science and technology, 2007,15 (1): 29 ~ 31) adopt ethylene glycol ethyl ether to replace common monohydric alcohol and refined edible soybeans oil to be raw material, prepared ethylene glycol ethyl ether soya-bean oil ethyl ester biodiesel by ester exchange reaction, products collection efficiency is about 90%; First reaction adds 310mL ethylene glycol ethyl ether and 2.4g sodium (being cut into small pieces) successively, until liquid level no longer includes floating sodium in 500mL conical flask.Afterwards in the 1000mL three-neck flask of cleaning installing thermometer and puddler, add the soya-bean oil that 530mL is pretreated, constant temperature after heating water bath to 90 DEG C, adds the alcohol sodium solution (heating 90 DEG C) of brand-new with vigorous stirring immediately, start to clock, vigorous stirring reaction 1h.After question response is complete, moved in 1000mL separatory funnel by the solution in flask, add dilute hydrochloric acid solution (90 DEG C) neutralization, static 24h, decompression distillation removing ethylene glycol ethyl ether, drying and dehydrating, obtains ethylene glycol ethyl ether soya-bean oil ethyl ester biodiesel.
The people such as ginger (Speciality Petrochemicals is in progress, 2008,9 (12): 41 ~ 43) are with refined palm oil, EGME for raw material, and sodium metal is catalyst, prepares a kind of novel biodiesel palm oil glycol methyl ether ester.In course of reaction, first sodium metal is dissolved in EGME and makes alcohol sodium solution, after refined palm oil and alcohol sodium solution are added in flask simultaneously, after question response is complete, moved into by the solution in flask in separatory funnel, watery hydrochloric acid neutralizes, static 24h, decompression distillation removing EGME, drying and dehydrating, obtains novel biodiesel palm oil glycol methyl ether ester.
The people such as Gao (Energy Fuel, 2011,25,4686 ~ 4692) with refined palm oil and glycol propyl ether for novel diesel palm oil glycol propyl ether monoesters prepared by raw material.By reaction raw materials refined palm oil and glycol propyl ether (alcohol oil rate 10: 1), sodium metal (mass ratio 1.2%) joins in the flask of 200mL, 80 DEG C of reaction 2h, rear rare HCl neutralization, decompression distillation and steam distillation remove unreacted palm oil and glycol monoethyl ether completely respectively, finally use the dehydration of 4A type molecular sieve drying, obtain novel diesel palm oil glycol propyl ether monoesters.
The people such as Zhang (International Journal of Green Energy, 2012,9 (7): 573 ~ 583) adopt refined palm oil and ethylene glycol monobutyl ether to carry out ester exchange reaction and prepare novel diesel palm oil butyl glycol ether monoesters.In course of reaction, first sodium metal is dissolved in ethylene glycol monobutyl ether and makes alcohol sodium solution, after refined palm oil and alcohol sodium solution are added in flask simultaneously, question response completely after, cooling, moved into by solution in flask in separatory funnel, watery hydrochloric acid neutralizes, static 24h, decompression distillation removing EGME, drying and dehydrating, obtain novel biodiesel palm oil glycol methyl ether ester, productive rate can reach 85.7%.
More than reaction is all catalyst with sodium metal.And feedstock oil needs the pretreatment such as strict refining depickling dewaters before reaction, after reacting completely, product needs hydrochloric acid to neutralize, static layering.Be separated except sub-cloud solution mainly glycerine and a small amount of soap.Unreacted ether is reclaimed in upper solution decompression distillation, suction filtration removing soda soap, and washing, desiccant dryness, obtain novel biodiesel repeatedly,
It is all homogeneous phase base catalyst that the novel biodiesel that above document is openly introduced prepares adopted catalyst, and its reactivity is not high, and last handling process is complicated, and product needs neutralization, washing, causes discharging a large amount of waste water, the problems such as contaminated environment.
Summary of the invention
The present invention is that will to solve the reactivity that homogeneous phase base catalyst that existing preparation novel biodiesel adopts exists not high, last handling process is complicated, product needs neutralization, washing, cause discharging a large amount of waste water, the problem of contaminated environment, and a kind of preparation method of ternary compound solid base catalyst is provided and utilizes it to catalyze and synthesize the method for novel biodiesel.
The preparation method of a kind of ternary compound solid base catalyst of the present invention, carries out according to the following steps:
One, x-KF/MO-MMT presoma is prepared: be that 1: 1 to join mass percent concentration be stir in the KF aqueous solution of 5% ~ 70% in mass ratio by alkaline earth oxide and sodium-based montmorillonite, control mixing speed is 100r/min ~ 120r/min, then place 2h, obtain x-KF/MO-MMT presoma; Described alkaline earth oxide and the gross mass of sodium-based montmorillonite and mass percent concentration are the volume ratio of the KF aqueous solution of 5% ~ 70% is 1g: 1mL;
Two, dry, roasting: x-KF/MO-MMT presoma step one prepared moves in baking oven, dry 12h at temperature is 80 DEG C, grinding, sieve through 100 orders, retain the lower sample of sieve, last is roasting 4h in 400 DEG C ~ 600 DEG C air atmospheres in temperature, namely obtains ternary compound solid base catalyst x-KF/MO-MMT.
Utilize above-mentioned ternary compound solid base catalyst to catalyze and synthesize the method for novel biodiesel, carry out according to the following steps:
By fatty acid methyl ester, poly glycol monomethyl ether and ternary compound solid base catalyst add in the reactor of band reflux condensate device, low whipping speed is 250r/min, reaction pressure is normal pressure, nitrogen protection and temperature are 60 DEG C ~ 150 DEG C condition lower magnetic force stirring reaction 2h ~ 10h, then be centrifugation 3min ~ 5min under the condition of 800r/min ~ 1000r/min at rotating speed, obtaining product is divided into two-layer, be separated the upper strata obtained and be novel biodiesel mixture, finally by the novel biodiesel mixture obtained decompression distillation 0.5h ~ 3h under temperature is 45 DEG C ~ 145 DEG C and vacuum is the condition of 0.1MPa, namely novel biodiesel is obtained, described poly glycol monomethyl ether and the mol ratio of fatty acid methyl ester are (1 ~ 20): 1, and described ternary compound solid base catalyst and the mass ratio of fatty acid methyl ester are (0.1 ~ 10): 100.
Advantage of the present invention:
1, ternary compound solid base catalyst of the present invention consists of potassium fluoride, alkaline earth oxide and imvite; Its preparation method is that potassium fluoride and alkaline earth oxide are introduced sodium-based montmorillonite, and modified imvite still maintains the distinctive layer structure of imvite, and potassium fluoride and alkaline earth oxide are dispersed on sodium-based montmorillonite;
2, to catalyze and synthesize the ternary compound solid base catalyst activity used in the method for novel biodiesel high in the present invention, when temperature is 60 DEG C ~ 150 DEG C, the conversion ratio of fatty acid methyl ester is the highest can reach 99%, higher than the associated catalysts reported in current document;
3, the present invention catalyzes and synthesizes in the method for novel biodiesel, the ternary compound solid base catalyst used effectively can resist water in reaction system, free fatty to the passivation of catalyst alkali position, post processing is simple, free from environmental pollution, meet the requirement of Green Chemistry, more suit industrial demand;
4, ternary compound solid base catalyst cheaper starting materials of the present invention is easy to get, and preparation process is simple, is easy to reclaim, reusable.
Accompanying drawing explanation
Fig. 1 is the SEM spectrogram of test one sodium-based montmorillonite used;
Fig. 2 be test one prepare ternary compound solid base catalyst 5%-KF/MgO-MMT SEM spectrogram;
Detailed description of the invention
Detailed description of the invention one: the preparation method of a kind of ternary compound solid base catalyst of present embodiment, carry out according to the following steps:
One, x-KF/MO-MMT presoma is prepared: be that 1: 1 to join mass percent concentration be stir in the KF aqueous solution of 5% ~ 70% in mass ratio by alkaline earth oxide and sodium-based montmorillonite, control mixing speed is 100r/min ~ 120r/min, then place 2h, obtain x-KF/MO-MMT presoma; Described alkaline earth oxide and the gross mass of sodium-based montmorillonite and mass percent concentration are the volume ratio of the KF aqueous solution of 5% ~ 70% is 1g: 1mL;
Two, dry, roasting: x-KF/MO-MMT presoma step one prepared moves in baking oven, dry 12h at temperature is 80 DEG C, grinding, sieve through 100 orders, retain the lower sample of sieve, last is roasting 4h in 400 DEG C ~ 600 DEG C air atmospheres in temperature, namely obtains ternary compound solid base catalyst x-KF/MO-MMT.
In ternary compound solid base catalyst x-KF/MO-MMT described in present embodiment, MO is alkaline earth oxide, and MMT is sodium-based montmorillonite, and x is the load capacity of KF on MO-MMT.
Ternary compound solid base catalyst described in present embodiment consists of potassium fluoride, alkaline earth oxide and imvite; Its preparation method is that potassium fluoride and alkaline earth oxide are introduced sodium-based montmorillonite, and modified imvite still maintains the distinctive layer structure of imvite, and potassium fluoride and alkaline earth oxide are dispersed on sodium-based montmorillonite.
Ternary compound solid base catalyst cheaper starting materials described in present embodiment is easy to get, and preparation process is simple, is easy to reclaim, reusable.
Detailed description of the invention two: present embodiment and detailed description of the invention one unlike: the alkaline earth oxide described in step one is magnesia, calcium oxide, strontium oxide strontia or barium monoxide.Other is identical with detailed description of the invention one.
Detailed description of the invention three: present embodiment and detailed description of the invention one or two unlike: the mass percent concentration of the KF aqueous solution described in step one is 5%.Other is identical with detailed description of the invention one or two.
Detailed description of the invention four: one of present embodiment and detailed description of the invention one to three unlike: the mass percent concentration of the KF aqueous solution described in step one is 20%.Other is identical with one of detailed description of the invention one to three.
Detailed description of the invention five: one of present embodiment and detailed description of the invention one to four unlike: the mass percent concentration of the KF aqueous solution described in step one is 30%.Other is identical with one of detailed description of the invention one to four.
Detailed description of the invention six: one of present embodiment and detailed description of the invention one to five unlike: the mass percent concentration of the KF aqueous solution described in step one is 70%.Other is identical with one of detailed description of the invention one to five.
Detailed description of the invention seven: present embodiment utilizes the ternary compound solid base catalyst of detailed description of the invention one to catalyze and synthesize the method for novel biodiesel, carries out according to the following steps:
By fatty acid methyl ester, poly glycol monomethyl ether and ternary compound solid base catalyst add in the reactor of band reflux condensate device, low whipping speed is 250r/min, reaction pressure is normal pressure, nitrogen protection and temperature are 60 DEG C ~ 150 DEG C condition lower magnetic force stirring reaction 2h ~ 10h, then be centrifugation 3min ~ 5min under the condition of 800r/min ~ 1000r/min at rotating speed, obtaining product is divided into two-layer, be separated the upper strata obtained and be novel biodiesel mixture, finally by the novel biodiesel mixture obtained decompression distillation 0.5h ~ 3h under temperature is 45 DEG C ~ 145 DEG C and vacuum is the condition of 0.1MPa, namely novel biodiesel is obtained, described poly glycol monomethyl ether and the mol ratio of fatty acid methyl ester are (1 ~ 20): 1, and described ternary compound solid base catalyst and the mass ratio of fatty acid methyl ester are (0.1 ~ 10): 100.
Present embodiment centrifugation is to remove solid catalyst, and decompression distillation is the methyl alcohol in order to be separated unreacted poly glycol monomethyl ether and generation.
Ternary compound solid base catalyst described in present embodiment consists of potassium fluoride, alkaline earth oxide and imvite; Its preparation method is that potassium fluoride and alkaline earth oxide are introduced sodium-based montmorillonite, and modified imvite still maintains the distinctive layer structure of imvite, and potassium fluoride and alkaline earth oxide are dispersed on sodium-based montmorillonite.
It is high that present embodiment catalyzes and synthesizes the ternary compound solid base catalyst activity used in the method for novel biodiesel, when temperature is 60 DEG C ~ 150 DEG C, the conversion ratio of fatty acid methyl ester is the highest can reach 99%, higher than the associated catalysts reported in current document.
Present embodiment catalyzes and synthesizes in the method for novel biodiesel, the ternary compound solid base catalyst used effectively can resist water in reaction system, free fatty to the passivation of catalyst alkali position, post processing is simple, free from environmental pollution, meet the requirement of Green Chemistry, more suit industrial demand.
Ternary compound solid base catalyst cheaper starting materials described in present embodiment is easy to get, and preparation process is simple, is easy to reclaim, reusable.
Detailed description of the invention eight: present embodiment and detailed description of the invention seven unlike: described fatty acid methyl ester is a kind of or wherein several mixture in methyl caprylate, methyl caprate, methyl laurate, myristic acid methyl esters, methyl hexadecanoate, methyl stearate, methyl oleate, methyl linoleate, methyl linolenate, methyl soyate and rapeseed oil fatty acid methyl esters.Other is identical with detailed description of the invention seven.
When fatty acid methyl ester described in present embodiment is mixture, be mixed by any ratio between each component.
Detailed description of the invention nine: present embodiment and detailed description of the invention seven or eight unlike: the structural formula general formula of described poly glycol monomethyl ether is: CH
3(OCH
2cH
2)
noH, wherein n is 1,2,3,4,5,7,9,10,15 or 20.Other is identical with detailed description of the invention seven or eight.
Adopt following verification experimental verification effect of the present invention:
Test one: a kind of preparation method of ternary compound solid base catalyst, carry out according to the following steps:
One, 5%-KF/MgO-MMT presoma is prepared: 5.0g magnesia and 5.0g sodium-based montmorillonite being joined simultaneously 10.0mL mass percent concentration is in the reaction bulb of the KF aqueous solution of 5%, be placed on magnetic stirring apparatus and stir, control mixing speed is 120r/min, then place 2h, obtain 5%-KF/MgO-MMT presoma.
Two, dry, roasting: 5%-KF/MgO-MMT presoma step one prepared moves in baking oven, dry 12h at temperature is 80 DEG C, grinding, sieve through 100 orders, retain the lower sample of sieve, last is roasting 4h in 500 DEG C of air atmospheres in temperature, namely obtains ternary compound solid base catalyst 5%-KF/MgO-MMT.
Scanning electron microscope diagram is in HIT S-4300 type field emission scanning electron microscope photographs, and voltage 20kV, sample vacuum chamber degree is better than 10
-4.Electron microscopic observation originally tests the surface topography of the ternary compound solid base catalyst of sodium-based montmorillonite used and this test preparation, result as depicted in figs. 1 and 2, Fig. 1 is that this tests the SEM spectrogram of sodium-based montmorillonite used, Fig. 2 is the SEM spectrogram of the ternary compound solid base catalyst 5%-KF/MgO-MMT of this test preparation, as shown in Figure 1, unclose balcony becomes the sheet of rule, and surface texture is regular, smooth unfolds, without edge-curl phenomenon; As shown in Figure 2, modified imvite still has laminar structured, and surface texture is no longer regular, has edge-curl phenomenon, and laminated structure edge is piled up, surface irregularity.
Test two: a kind of preparation method of ternary compound solid base catalyst, carry out according to the following steps:
One, 35%-KF/MgO-MMT presoma is prepared: 5.0g magnesia and 5.0g sodium-based montmorillonite being joined simultaneously 10.0mL mass percent concentration is in the reaction bulb of the KF aqueous solution of 35%, be placed on magnetic stirring apparatus and stir, control mixing speed is 120r/min, then place 2h, obtain 35%-KF/MgO-MMT presoma;
Two, dry, roasting: 35%-KF/MgO-MMT presoma step one prepared moves in baking oven, dry 12h at temperature is 80 DEG C, grinding, sieve through 100 orders, retain the lower sample of sieve, last is roasting 4h in 500 DEG C of air atmospheres in temperature, namely obtains ternary compound solid base catalyst 35%-KF/MgO-MMT.
Test three: a kind of preparation method of ternary compound solid base catalyst, carry out according to the following steps:
One, 30%-KF/CaO-MMT presoma is prepared: 5.0g calcium oxide and 5.0g sodium-based montmorillonite being joined simultaneously 10.0mL mass percent concentration is in the reaction bulb of the KF aqueous solution of 30%, be placed on magnetic stirring apparatus and stir, control mixing speed is 120r/min, then place 2h, obtain 30%-KF/CaO-MMT presoma;
Two, dry, roasting: 30%-KF/CaO-MMT presoma step one prepared moves in baking oven, dry 12h at temperature is 80 DEG C, grinding, sieve through 100 orders, retain the lower sample of sieve, last is roasting 4h in 500 DEG C of air atmospheres in temperature, namely obtains ternary compound solid base catalyst 30%-KF/CaO-MMT.
Test four: a kind of preparation method of ternary compound solid base catalyst, carry out according to the following steps:
One, 50%-KF/CaO-MMT presoma is prepared: 5.0g calcium oxide and 5.0g sodium-based montmorillonite being joined simultaneously 10.0mL mass percent concentration is in the reaction bulb of the KF aqueous solution of 50%, be placed on magnetic stirring apparatus and stir, control mixing speed is 120r/min, then place 2h, obtain 50%-KF/CaO-MMT presoma;
Two, dry, roasting: 50%-KF/CaO-MMT presoma step one prepared moves in baking oven, dry 12h at temperature is 80 DEG C, grinding, sieve through 100 orders, retain the lower sample of sieve, last is roasting 4h in 500 DEG C of air atmospheres in temperature, namely obtains ternary compound solid base catalyst 50%-KF/CaO-MMT.
Test five: a kind of preparation method of ternary compound solid base catalyst, carry out according to the following steps:
One, 20%-KF/CaO-MMT presoma is prepared: 5.0g calcium oxide and 5.0g sodium-based montmorillonite being joined simultaneously 10.0mL mass percent concentration is in the reaction bulb of the KF aqueous solution of 20%, be placed on magnetic stirring apparatus and stir, control mixing speed is 120r/min, then place 2h, obtain 20%-KF/CaO-MMT presoma;
Two, dry, roasting: 20%-KF/CaO-MMT presoma step one prepared moves in baking oven, dry 12h at temperature is 80 DEG C, grinding, sieve through 100 orders, retain the lower sample of sieve, last is roasting 4h in 500 DEG C of air atmospheres in temperature, namely obtains ternary compound solid base catalyst 20%-KF/CaO-MMT.
Test six: a kind of preparation method of ternary compound solid base catalyst, carry out according to the following steps:
One, 40%-KF/SrO-MMT presoma is prepared: 5.0g strontium oxide strontia and 5.0g sodium-based montmorillonite being joined simultaneously 10.0mL mass percent concentration is in the reaction bulb of the KF aqueous solution of 40%, be placed on magnetic stirring apparatus and stir, control mixing speed is 120r/min, then place 2h, obtain 40%-KF/SrO-MMT presoma;
Two, dry, roasting: 40%-KF/SrO-MMT presoma step one prepared moves in baking oven, dry 12h at temperature is 80 DEG C, grinding, sieve through 100 orders, retain the lower sample of sieve, last is roasting 4h in 500 DEG C of air atmospheres in temperature, namely obtains ternary compound solid base catalyst 40%-KF/SrO-MMT.
Test seven: a kind of preparation method of ternary compound solid base catalyst, carry out according to the following steps:
One, 25%-KF/SrO-MMT presoma is prepared: 5.0g strontium oxide strontia and 5.0g sodium-based montmorillonite being joined simultaneously 10.0mL mass percent concentration is in the reaction bulb of the KF aqueous solution of 25%, be placed on magnetic stirring apparatus and stir, control mixing speed is 120r/min, then place 2h, obtain 25%-KF/SrO-MMT presoma;
Two, dry, roasting: 25%-KF/SrO-MMT presoma step one prepared moves in baking oven, dry 12h at temperature is 80 DEG C, grinding, sieve through 100 orders, retain the lower sample of sieve, last is roasting 4h in 500 DEG C of air atmospheres in temperature, namely obtains ternary compound solid base catalyst 25%-KF/SrO-MMT.
Test eight: a kind of preparation method of ternary compound solid base catalyst, carry out according to the following steps:
One, 70%-KF/SrO-MMT presoma is prepared: 5.0g strontium oxide strontia and 5.0g sodium-based montmorillonite being joined simultaneously 10.0mL mass percent concentration is in the reaction bulb of the KF aqueous solution of 70%, be placed on magnetic stirring apparatus and stir, control mixing speed is 120r/min, then place 2h, obtain 70%-KF/SrO-MMT presoma;
Two, dry, roasting: 70%-KF/SrO-MMT presoma step one prepared moves in baking oven, dry 12h at temperature is 80 DEG C, grinding, sieve through 100 orders, retain the lower sample of sieve, last is roasting 4h in 500 DEG C of air atmospheres in temperature, namely obtains ternary compound solid base catalyst 70%-KF/SrO-MMT.
Test nine: the ternary compound solid base catalyst utilizing test two to prepare catalyzes and synthesizes the method for novel biodiesel, carries out according to the following steps:
By 5.0g methyl soyate (0.016mol), the 35%-KF/MgO-MMT catalyst of 12.2g glycol monoethyl ether (0.16mol) and methyl soyate quality 5% joins in the there-necked flask with condensing reflux, low whipping speed is 250r/min, reaction pressure is normal pressure, nitrogen protection and temperature are 120 DEG C of condition lower magnetic force stirring reaction 6h, then be centrifugation 3min under the condition of 1000r/min at rotating speed, obtaining product is divided into two-layer, be separated except sub-cloud 35%-KF/MgO-MMT catalyst, be separated the upper strata obtained and be novel biodiesel mixture, finally by the novel biodiesel mixture obtained decompression distillation 0.5h under temperature is 45 DEG C and vacuum is the condition of 0.1MPa, be separated the methyl alcohol of unreacted glycol monoethyl ether and generation, namely novel biodiesel is obtained---soybean oil glycol monoethyl ether ester.
By FID gas chromatographic analysis, novel biodiesel---the productive rate of soybean oil glycol monoethyl ether ester can reach 96%.
Test ten: the ternary compound solid base catalyst utilizing test three to prepare catalyzes and synthesizes the method for novel biodiesel, carries out according to the following steps:
By 5.0g rapeseed oil fatty acid methyl esters (0.016mol), the 30%-KF/CaO-MMT catalyst of 19.2g diethylene glycol monomethyl ether (0.16mol) and rapeseed oil fatty acid methyl esters quality 5% joins in the there-necked flask with reflux condensate device, low whipping speed is 250r/min, reaction pressure is normal pressure, nitrogen protection and temperature are 120 DEG C of condition lower magnetic force stirring reaction 6h, then be centrifugation 3min under the condition of 1000r/min at rotating speed, obtaining product is divided into two-layer, be separated except sub-cloud 30%-KF/CaO-MMT catalyst, be separated the upper strata obtained and be novel biodiesel mixture, finally by the novel biodiesel mixture obtained decompression distillation 1h under temperature is 75 DEG C and vacuum is the condition of 0.1MPa, decompression distillation is separated the methyl alcohol of unreacted diethylene glycol monomethyl ether and generation, namely novel biodiesel is obtained---rapeseed oil diethylene glycol monomethyl ether ester.
By FID gas chromatographic analysis, novel biodiesel---the productive rate of rapeseed oil diethylene glycol monomethyl ether ester can reach 98%.
Test 11: the ternary compound solid base catalyst utilizing test seven to prepare catalyzes and synthesizes the method for novel biodiesel, carry out according to the following steps:
By 5.0g methyl laurate (0.023mol), the 25%-KF/SrO-MMT catalyst of 9.6g triethylene glycol monomethyl ether (0.046mol) and methyl laurate quality 5% joins in the there-necked flask with reflux condensate device, low whipping speed is 250r/min, reaction pressure is normal pressure, nitrogen protection and temperature are 120 DEG C of condition lower magnetic force stirring reaction 6h, then be centrifugation 3min under the condition of 1000r/min at rotating speed, obtaining product is divided into two-layer, be separated except sub-cloud 25%-KF/SrO-MMT catalyst, be separated the upper strata obtained and be novel biodiesel mixture, finally by the novel biodiesel mixture obtained decompression distillation 1.5h under temperature is 100 DEG C and vacuum is the condition of 0.1MPa, decompression distillation is separated the methyl alcohol of unreacted triethylene glycol monomethyl ether and generation, namely novel biodiesel is obtained---laurate triethylene glycol monomethyl ether ester.
By FID gas chromatographic analysis, novel biodiesel---the productive rate of laurate triethylene glycol monomethyl ether ester can reach 99%.
Existing COMPARATIVE CATALYST's test:
The control group of test nine: the method being Material synthesis novel biodiesel with methyl soyate and glycol monoethyl ether, carries out according to the following steps:
One, the preparation of potassium alkoxide solution: add 12.2g glycol monoethyl ether and 0.04g potassium hydroxide in 100mL conical flask successively, mixing concussion is dissolved completely to potassium hydroxide, obtains potassium alkoxide solution;
Two, ester exchange reaction: 5.0g methyl soyate (0.016mol) is joined in the there-necked flask with condensing reflux, nitrogen protection, constant temperature after heating water bath to 60 DEG C, potassium alkoxide solution (being heated to 60 DEG C) prepared by step one is added under vigorous stirring, reaction 2h, move into after product cooling in 1000mL separatory funnel, add 10% dilute hydrochloric acid solution neutralization, to solution in neutral, be separated removing lower floor aqueous phase, upper solution saturated NaCl solution (150mL) washes 3 times, be separated, removing lower floor aqueous phase, upper solution decompression distillation is separated the methyl alcohol of unreacted glycol monoethyl ether and generation, dry, obtain novel biodiesel---soybean oil glycol monoethyl ether ester.
By FID gas chromatographic analysis, the productive rate of novel biodiesel---soybean oil glycol monoethyl ether ester is 83%.
Test the control group of 11: the method being Material synthesis two generation biodiesel with methyl laurate and triethylene glycol monomethyl ether, carry out according to the following steps:
One, the preparation of alcohol sodium solution: add 12.2g glycol monoethyl ether and 0.025g sodium in 100mL conical flask successively, until liquid level no longer includes floating sodium, obtains alcohol sodium solution;
Two, ester exchange reaction: by 5.0g methyl laurate (0.023mol), join in the there-necked flask with reflux condensate device, constant temperature after heating water bath to 90 DEG C, alcohol sodium solution (being heated to 90 DEG C) prepared by step one is added under vigorous stirring, reaction 2h, product moves in 1000mL separatory funnel, add 10% dilute hydrochloric acid solution neutralization, to solution in neutral, be separated removing lower floor aqueous phase, upper strata saturated NaCl solution (150mL) washes 3 times, separatory removing lower floor aqueous phase, the methyl alcohol of unreacted glycol monoethyl ether and generation is reclaimed in upper solution decompression distillation, dry, obtain faint yellow clear product, i.e. novel biodiesel---laurate triethylene glycol monomethyl ether ester.
By FID gas chromatographic analysis, the productive rate of novel biodiesel---laurate triethylene glycol monomethyl ether ester is 81%.
Claims (8)
1. a preparation method for ternary compound solid base catalyst, is characterized in that the preparation method of ternary compound solid base catalyst carries out according to the following steps:
One, x-KF/MO-MMT presoma is prepared: be stir in the KF aqueous solution of 5% ~ 70% for 1:1 joins mass percent concentration in mass ratio by alkaline earth oxide and sodium-based montmorillonite, control mixing speed is 100r/min ~ 120r/min, then place 2h, obtain x-KF/MO-MMT presoma; Described alkaline earth oxide and the gross mass of sodium-based montmorillonite and mass percent concentration are the volume ratio of the KF aqueous solution of 5% ~ 70% is 1g:1mL;
Two, dry, roasting: x-KF/MO-MMT presoma step one prepared moves in baking oven, dry 12h at temperature is 80 DEG C, grinding, sieve through 100 orders, retain the lower sample of sieve, last is roasting 4h in 400 DEG C ~ 600 DEG C air atmospheres in temperature, namely obtains ternary compound solid base catalyst x-KF/MO-MMT;
Alkaline earth oxide described in step one is magnesia, calcium oxide, strontium oxide strontia or barium monoxide.
2. the preparation method of a kind of ternary compound solid base catalyst according to claim 1, is characterized in that the mass percent concentration of the KF aqueous solution described in step one is 5%.
3. the preparation method of a kind of ternary compound solid base catalyst according to claim 1, is characterized in that the mass percent concentration of the KF aqueous solution described in step one is 20%.
4. the preparation method of a kind of ternary compound solid base catalyst according to claim 1, is characterized in that the mass percent concentration of the KF aqueous solution described in step one is 30%.
5. the preparation method of a kind of ternary compound solid base catalyst according to claim 1, is characterized in that the mass percent concentration of the KF aqueous solution described in step one is 70%.
6. the ternary compound solid base catalyst utilizing preparation method as claimed in claim 1 to prepare catalyzes and synthesizes the method for novel biodiesel, it is characterized in that the method utilizing ternary compound solid base catalyst to catalyze and synthesize novel biodiesel is carried out according to the following steps:
By fatty acid methyl ester, poly glycol monomethyl ether and ternary compound solid base catalyst add in the reactor of band reflux condensate device, low whipping speed is 250r/min, reaction pressure is normal pressure, nitrogen protection and temperature are 60 DEG C ~ 150 DEG C condition lower magnetic force stirring reaction 2h ~ 10h, then be centrifugation 3min ~ 5min under the condition of 800r/min ~ 1000r/min at rotating speed, obtaining product is divided into two-layer, be separated the upper strata obtained and be novel biodiesel mixture, finally by the novel biodiesel mixture obtained decompression distillation 0.5h ~ 3h under temperature is 45 DEG C ~ 145 DEG C and vacuum is the condition of 0.1MPa, namely novel biodiesel is obtained, described poly glycol monomethyl ether and the mol ratio of fatty acid methyl ester are (1 ~ 20): 1, and described ternary compound solid base catalyst and the mass ratio of fatty acid methyl ester are (0.1 ~ 10): 100,
Described novel biodiesel refers to introduces ether by ester exchange reaction and the higher fuel of the oxygen content that generates on the basis of biodiesel and fatty acid methyl ester.
7. the method utilizing ternary compound solid base catalyst to catalyze and synthesize novel biodiesel according to claim 6, is characterized in that described fatty acid methyl ester is a kind of or wherein several mixture in methyl caprylate, methyl caprate, methyl laurate, myristic acid methyl esters, methyl hexadecanoate, methyl stearate, methyl oleate, methyl linoleate, methyl linolenate, methyl soyate and rapeseed oil fatty acid methyl esters.
8. the method utilizing ternary compound solid base catalyst to catalyze and synthesize novel biodiesel according to claim 6, is characterized in that the structural formula general formula of described poly glycol monomethyl ether is: CH
3(OCH
2cH
2)
noH, wherein n is 2,3,4,5,7,9,10,15 or 20.
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