CN103301857A - 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 new bio diesel oil.
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 that made through ester exchange reaction by animal and plant fat (fatty acid triglycercide) and short chain alcohol (methyl alcohol or ethanol).
Formula 1 biodiesel ester exchange reaction equation
R in the following formula
1, R
2, R
3Be C
12～24The straight-chain alkyl of (saturated or unsaturated), ROH represents lower aliphatic alcohols, adopts methyl alcohol and ethanol more, wherein mostly to be mixed glyceride (be R to glyceride
1≠ R
2Perhaps ≠ R
3).It has characteristics such as biodegradable, renewable, environmental friendliness biodiesel, but only contains an ester group in its molecular structure, and oxygen content is lower, and burning and discharge performance are not ideal enough.Therefore, to the further modification of biodiesel, all very important for the development of development China's grease and related industries.
New bio diesel oil refers to introduce the higher fuel of oxygen content that ether generates by ester exchange reaction on the basis of biodiesel (fatty acid methyl ester).
Formula 2 new bio diesel oil ester exchange reaction equations
New bio diesel oil ester (n=1,2,3,4,5,7,9,10,15,20) in the following formula is that fatty acid methyl ester (FAME) is compared with traditional biodiesel, new bio diesel oil 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 advantages such as oxidation stability suitable with diesel oil.Simultaneously, new bio diesel oil is owing to the introducing of ether, and oxygen content increases, and it is more complete to burn, and that can effectively reduce restriction (comprises CO with unrestriced pollutant emission
2, SO
x, NO
x), can also reduce discharge quantity of particulate matter.Because new bio diesel oil has many-sided advantage than biodiesel, therefore, the research of new bio diesel oil will receive increasing concern.
People such as Jiang (Journal of Biomedicine and Biotechnology, 2011,2011,1～8) adopt refining rapeseed oil, and glycol monoethyl ether is raw material, and KOH is catalyst, and ester exchange reaction has prepared new bio diesel oil rapeseed oil monoesters.Before the reaction beginning, at first remove aliphatic acid with ethanol at 90 ℃ of following preliminary treatment rapeseed oils, vacuum is purified and is removed ethanol.Infrared detection is determined aliphatic acid, and ethanol is removed fully.600mL makes with extra care rapeseed oil, 250mL glycol monoethyl ether, 0.6%KOH catalyst, 65 ℃ of reactions.After reacting completely, thick product neutralizes with rare HCl, separates and removes water, and vacuum is purified, and removes glycol monoethyl ether, CaCl
2Drying gets new bio diesel oil rapeseed oil monoesters.
People such as Lee (contemporary chemical industry, 2012,41 (2): 116～119) adopt refining cottonseed oil and diethylene glycol monomethyl ether to carry out ester exchange reaction and prepared new bio diesel oil cottonseed oil diethylene glycol dimethyl ether ester.Building-up process: the 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 product methyl alcohol in the course of reaction and guarantee that reaction continues forward and carries out, the sign reaction finishes when no liquid oozes in the condenser pipe.The cooling back moves in the separatory funnel, adds the dilute hydrochloric acid solution neutralization and removes KOH, and with saturated NaCl aqueous solution washing 2～3 times, unnecessary diethylene glycol dimethyl ether and water are removed in decompression distillation then, and end product is cottonseed oil diethylene glycol dimethyl ether ester.
(African Journal of Biotechnology, 2011,10 (72): 16300～16313) adopt refining palm oil and glycol monoethyl ether is raw material to people such as Jiang, and KOH is catalyst, and ester exchange reaction has prepared palm oil glycol monoethyl ether ester.Before the reaction, at first remove aliphatic acid with ethanol at 90 ℃ of following preliminary treatment palm oils, vacuum is purified and is removed ethanol.Infrared detection is determined free fatty, and ethanol is removed fully.600mL makes with extra care palm oil, 210mL glycol monoethyl ether, 0.6%KOH catalyst, 80 ℃ of reactions.After reacting completely, thick product neutralizes with rare HCl, separates and removes water, and vacuum is purified, and removes glycol monoethyl ether, CaCl
2Drying gets new bio diesel oil palm oil monoesters, and productive rate can reach 85%.
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 prepared novel diesel cottonseed oil glycol monoethyl ether ester.With a certain amount of refining cottonseed oil and glycol monoethyl ether (, alcohol oil rate 8: 1), 1% (percent by volume) KOH adds in the flask, 90 ℃ of reaction 2h.The rare HCl neutralization in back, decompression distillation and steam distillation are removed unreacted cottonseed oil and glycol monoethyl ether completely respectively, use the dehydration of 4A type molecular sieve drying at last, get novel diesel cottonseed oil glycol monoethyl ether ester.
(regenerative resource, 2007,25 (1): 32～35) adopt refining rapeseed oil and glycol monoethyl ether is raw material to people such as Jiang, prepares a kind of new bio diesel oil, the rapeseed oil glycol methyl ether ester.Join in the there-necked flask of 1000mL after a certain amount of rapeseed oil depickling dewatered, when temperature in the container is 60 ℃ when constant, add the potassium alkoxide solution for preparing, treat fully reaction after, solution in the flask is transferred in the separatory funnel, added appropriate hydrochloric acid and make solution be neutral.Leave standstill 12h, layering, remove the crude glycerine of separatory funnel lower floor yellowish-brown thickness after, just obtain coarse biodiesel.Except excessive glycol monoethyl ether in the dereaction, the soap salt that suction filtration produces except dereaction through washing and dry repeatedly, gets end product rapeseed oil glycol methyl ether ester again by decompression distillation, and productive rate can reach 84%.
Above document all is to be catalyst with KOH, and feedstock oil needs preliminary treatment such as depickling dewaters, after reacting completely, product need move in the separatory funnel and to add the dilute hydrochloric acid solution neutralization and remove KOH, saturated NaCl solution washing, post processings such as decompression distillation, end product is new bio diesel oil.
Open and wait people's (oil and foodstuffs science and technology, 2007,15 (1): 29～31) adopting ethylene glycol ethyl ether to replace common monohydric alcohol and refined edible soybean oil is raw material, has prepared ethylene glycol ethyl ether soya-bean oil ethyl ester biodiesel by ester exchange reaction, and the product productive rate is about 90%; Reaction at first adds 310mL ethylene glycol ethyl ether and 2.4g sodium (being cut into small pieces) successively in the 500mL conical flask, till liquid level no longer includes unsteady sodium.Afterwards in the 1000mL three-neck flask of the cleaning that thermometer and puddler are installed, add the pretreated soya-bean oil of 530mL, constant temperature after water-bath is heated to 90 ℃ adds the pure sodium solution (heating 90 ℃) of new system immediately under vigorous stirring, begin to clock vigorous stirring reaction 1h.After question response is complete, the solution in the flask is moved in the 1000mL separatory funnel, add dilute hydrochloric acid solution (90 ℃) neutralization, static 24h, ethylene glycol ethyl ether is removed in decompression distillation, and drying and dehydrating gets ethylene glycol ethyl ether soya-bean oil ethyl ester biodiesel.
(the Speciality Petrochemicals progress, 2008,9 (12): be raw material with refining palm oil, EGME 41～43), sodium metal is catalyst to people such as ginger, prepares a kind of new bio diesel oil palm oil glycol methyl ether ester.In the course of reaction, earlier sodium metal is dissolved in EGME and makes pure sodium solution, after will make with extra care palm oil and pure sodium solution adds in the flask simultaneously, after question response is complete, the solution in the flask is moved in the separatory funnel watery hydrochloric acid neutralization, static 24h, EGME is removed in decompression distillation, and drying and dehydrating gets new bio diesel oil palm oil glycol methyl ether ester.
People such as Gao (Energy Fuel, 2011,25,4686～4692) are that feedstock production goes out novel diesel palm oil glycol propyl ether monoesters with refining palm oil and glycol propyl ether.With the refining palm oil of reaction raw materials and glycol propyl ether (alcohol oil rate 10: 1), sodium metal (mass ratio 1.2%) joins in the flask of 200mL, 80 ℃ of reaction 2h, the rare HCl neutralization in back, decompression distillation and steam distillation are removed unreacted palm oil and glycol monoethyl ether completely respectively, use the dehydration of 4A type molecular sieve drying at last, get novel diesel palm oil glycol propyl ether monoesters.
People such as Zhang (International Journal of Green Energy, 2012,9 (7): 573～583) adopt refining palm oil and ethylene glycol monobutyl ether to carry out ester exchange reaction and prepared novel diesel palm oil butyl glycol ether monoesters.In the course of reaction, earlier sodium metal is dissolved in ethylene glycol monobutyl ether and makes pure sodium solution, after will make with extra care palm oil and pure sodium solution adds in the flask simultaneously, question response fully after, cooling, solution in the flask is moved in the separatory funnel watery hydrochloric acid neutralization, static 24h, EGME is removed in decompression distillation, drying and dehydrating gets new bio diesel oil palm oil glycol methyl ether ester, and productive rate can reach 85.7%.
More than reaction all is catalyst with the sodium metal.And feedstock oil needs preliminary treatment such as strict refining depickling dewaters before the reaction, and after reacting completely, product needs hydrochloric acid neutralization, static layering.Separation mainly is glycerine and a spot of soap except sub-cloud solution.Unreacted ether is reclaimed in the upper solution decompression distillation, and suction filtration is removed soda soap, and washing, drier drying get new bio diesel oil repeatedly,
The catalyst that the new bio diesel oil preparation that above document is openly introduced is adopted all is the homogeneous phase base catalyst, and its reactivity is not high, and last handling process complexity, product need neutralization, washing, cause discharging a large amount of waste water, 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 new bio diesel oil adopts exists not high, the last handling process complexity, product needs neutralization, washing, cause discharging a large amount of waste water, problem of environment pollution caused, and a kind of preparation method of ternary complex solid base catalyst is provided and utilizes it to catalyze and synthesize the method for new bio diesel oil.
The preparation method of a kind of ternary complex solid of the present invention base catalyst, carry out according to the following steps:
One, preparation x-KF/MO-MMT presoma: be that to join mass percent concentration at 1: 1 be to stir in 5%～70% the KF aqueous solution by mass ratio with alkaline earth oxide and sodium-based montmorillonite, the control mixing speed is 100r/min～120r/min, place 2h then, obtain the x-KF/MO-MMT presoma; The gross mass of described alkaline earth oxide and sodium-based montmorillonite and mass percent concentration are that the volume ratio of 5%～70% the KF aqueous solution is 1g: 1mL;
Two, dry, roasting: the x-KF/MO-MMT presoma of step 1 preparation is moved in the baking oven, dry 12h under temperature is 80 ℃, grind, sieve through 100 orders, keep sieve sample down, be roasting 4h in 400 ℃～600 ℃ air atmospheres in temperature at last, namely obtain ternary complex solid base catalyst x-KF/MO-MMT.
Utilize above-mentioned ternary complex solid base catalyst to catalyze and synthesize the method for new bio diesel oil, carry out according to the following steps:
With fatty acid methyl ester, poly glycol monomethyl ether and ternary complex solid base catalyst add in the reactor of taking back the stream condensing unit, low whipping speed is 250r/min, reaction pressure is normal pressure, nitrogen protection and temperature are 60 ℃～150 ℃ condition lower magnetic force stirring reaction 2h～10h, be centrifugation 3min～5min under the condition of 800r/min～1000r/min at rotating speed then, obtaining product is divided into two-layer, separate the upper strata that obtains and be the new bio diesel fuel mixtures, be that 45 ℃～145 ℃ and vacuum are decompression distillation 0.5h～3h under the condition of 0.1MPa with the new bio diesel fuel mixtures that obtains in temperature at last, namely obtain new bio diesel oil; The mol ratio of described poly glycol monomethyl ether and fatty acid methyl ester is (1～20): 1, and the mass ratio of described ternary complex solid base catalyst and fatty acid methyl ester is (0.1～10): 100.
Advantage of the present invention:
1, ternary complex 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 the imvite after the modification has still kept the distinctive layer structure of imvite, and potassium fluoride and alkaline earth oxide are dispersed on the sodium-based montmorillonite;
2, the present invention catalyzes and synthesizes the active height of the ternary complex solid base catalyst that uses in the method for new bio diesel oil, when temperature is 60 ℃～150 ℃, the conversion ratio of fatty acid methyl ester is the highest can to reach 99%, is higher than the associated catalysts of having reported in the present document;
3, the present invention catalyzes and synthesizes in the method for new bio diesel oil, the ternary complex solid base catalyst that uses can effectively be resisted water in the 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 complex solid base catalyst raw material of the present invention is cheap and easy to get, and preparation process is simple, is easy to reclaim, and is reusable.
Description of drawings
Fig. 1 is the SEM spectrogram of test one used sodium-based montmorillonite;
Fig. 2 for the test one the preparation ternary complex solid base catalyst 5%-KF/MgO-MMT the SEM spectrogram;
The specific embodiment
The specific embodiment one: the preparation method of a kind of ternary complex solid of present embodiment base catalyst, carry out according to the following steps:
One, preparation x-KF/MO-MMT presoma: be that to join mass percent concentration at 1: 1 be to stir in 5%～70% the KF aqueous solution by mass ratio with alkaline earth oxide and sodium-based montmorillonite, the control mixing speed is 100r/min～120r/min, place 2h then, obtain the x-KF/MO-MMT presoma; The gross mass of described alkaline earth oxide and sodium-based montmorillonite and mass percent concentration are that the volume ratio of 5%～70% the KF aqueous solution is 1g: 1mL;
Two, dry, roasting: the x-KF/MO-MMT presoma of step 1 preparation is moved in the baking oven, dry 12h under temperature is 80 ℃, grind, sieve through 100 orders, keep sieve sample down, be roasting 4h in 400 ℃～600 ℃ air atmospheres in temperature at last, namely obtain ternary complex solid base catalyst x-KF/MO-MMT.
MO is alkaline earth oxide among the described ternary complex solid of the present embodiment base catalyst x-KF/MO-MMT, and MMT is sodium-based montmorillonite, and x is the load capacity of KF on MO-MMT.
The described ternary complex solid of present embodiment base catalyst 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 the imvite after the modification has still kept the distinctive layer structure of imvite, and potassium fluoride and alkaline earth oxide are dispersed on the sodium-based montmorillonite.
The described ternary complex solid of present embodiment base catalyst raw material is cheap and easy to get, and preparation process is simple, is easy to reclaim, and is reusable.
The specific embodiment two: what present embodiment and the specific embodiment one were different is: the alkaline earth oxide described in the step 1 is magnesia, calcium oxide, strontium oxide strontia or barium monoxide.Other is identical with the specific embodiment one.
The specific embodiment three: what present embodiment was different with the specific embodiment one or two is: the mass percent concentration of the KF aqueous solution described in the step 1 is 5%.Other is identical with the specific embodiment one or two.
The specific embodiment four: what present embodiment was different with one of specific embodiment one to three is: the mass percent concentration of the KF aqueous solution described in the step 1 is 20%.Other is identical with one of specific embodiment one to three.
The specific embodiment five: what present embodiment was different with one of specific embodiment one to four is: the mass percent concentration of the KF aqueous solution described in the step 1 is 30%.Other is identical with one of specific embodiment one to four.
The specific embodiment six: what present embodiment was different with one of specific embodiment one to five is: the mass percent concentration of the KF aqueous solution described in the step 1 is 70%.Other is identical with one of specific embodiment one to five.
The specific embodiment seven: present embodiment utilizes the ternary complex solid base catalyst of the specific embodiment one to catalyze and synthesize the method for new bio diesel oil, carries out according to the following steps:
With fatty acid methyl ester, poly glycol monomethyl ether and ternary complex solid base catalyst add in the reactor of taking back the stream condensing unit, low whipping speed is 250r/min, reaction pressure is normal pressure, nitrogen protection and temperature are 60 ℃～150 ℃ condition lower magnetic force stirring reaction 2h～10h, be centrifugation 3min～5min under the condition of 800r/min～1000r/min at rotating speed then, obtaining product is divided into two-layer, separate the upper strata that obtains and be the new bio diesel fuel mixtures, be that 45 ℃～145 ℃ and vacuum are decompression distillation 0.5h～3h under the condition of 0.1MPa with the new bio diesel fuel mixtures that obtains in temperature at last, namely obtain new bio diesel oil; The mol ratio of described poly glycol monomethyl ether and fatty acid methyl ester is (1～20): 1, and the mass ratio of described ternary complex solid base catalyst and fatty acid methyl ester is (0.1～10): 100.
The present embodiment centrifugation is in order to remove solid catalyst, and decompression distillation is in order to separate the methyl alcohol of unreacted poly glycol monomethyl ether and generation.
The described ternary complex solid of present embodiment base catalyst 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 the imvite after the modification has still kept the distinctive layer structure of imvite, and potassium fluoride and alkaline earth oxide are dispersed on the sodium-based montmorillonite.
It is active high that present embodiment catalyzes and synthesizes the ternary complex solid base catalyst that uses in the method for new bio diesel oil, when temperature is 60 ℃～150 ℃, the conversion ratio of fatty acid methyl ester is the highest can to reach 99%, is higher than the associated catalysts of having reported in the present document.
Present embodiment catalyzes and synthesizes in the method for new bio diesel oil, the ternary complex solid base catalyst that uses can effectively be resisted water in the 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.
The described ternary complex solid of present embodiment base catalyst raw material is cheap and easy to get, and preparation process is simple, is easy to reclaim, and is reusable.
The specific embodiment eight: what present embodiment and the specific embodiment seven were different is: described fatty acid methyl ester is a kind of in methyl caprylate, methyl caprate, methyl laurate, myristic acid methyl esters, methyl hexadecanoate, methyl stearate, methyl oleate, methyl linoleate, methyl linolenate, methyl soyate and the rapeseed oil fatty acid methyl esters or several mixture wherein.Other is identical with the specific embodiment seven.
When the described fatty acid methyl ester of present embodiment is mixture, press between each component arbitrarily than mixing.
The specific embodiment nine: what present embodiment was different with the specific embodiment seven or eight is: 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 the specific embodiment seven or eight.
Adopt following verification experimental verification effect of the present invention:
Test one: a kind of preparation method of ternary complex solid base catalyst, carry out according to the following steps:
One, preparation 5%-KF/MgO-MMT presoma: 5.0g magnesia and 5.0g sodium-based montmorillonite are joined in the reaction bulb that the 10.0mL mass percent concentration is 5% the KF aqueous solution simultaneously, place on the magnetic stirring apparatus and stir, the control mixing speed is 120r/min, place 2h then, obtain the 5%-KF/MgO-MMT presoma.
Two, dry, roasting: the 5%-KF/MgO-MMT presoma of step 1 preparation is moved in the baking oven, dry 12h under temperature is 80 ℃, grind, sieve through 100 orders, keep sieve sample down, be roasting 4h in 500 ℃ of air atmospheres in temperature at last, namely obtain ternary complex solid base catalyst 5%-KF/MgO-MMT.
Scanning electron microscope diagram is in the S-4300 of HIT type field emission scanning electron microscope photographs, voltage 20kV, and the sample vacuum chamber degree is better than 10
-4Electron microscopic observation is originally tested the surface topography of the ternary complex solid base catalyst of used sodium-based montmorillonite and this test preparation, the result as depicted in figs. 1 and 2, Fig. 1 tests the SEM spectrogram of used sodium-based montmorillonite for this, Fig. 2 is the SEM spectrogram of the ternary complex solid base catalyst 5%-KF/MgO-MMT of this test preparation, as shown in Figure 1, unmodified imvite becomes the sheet of rule, and surface texture is regular, smooth unfolds no edge-curl phenomenon; As shown in Figure 2, the imvite after the modification still has laminar structured, and surface texture is no longer regular, and edge-curl phenomenon is arranged, and the laminated structure edge is piled up, surface irregularity.
Test two: a kind of preparation method of ternary complex solid base catalyst, carry out according to the following steps:
One, preparation 35%-KF/MgO-MMT presoma: 5.0g magnesia and 5.0g sodium-based montmorillonite are joined in the reaction bulb that the 10.0mL mass percent concentration is 35% the KF aqueous solution simultaneously, place on the magnetic stirring apparatus and stir, the control mixing speed is 120r/min, place 2h then, obtain the 35%-KF/MgO-MMT presoma;
Two, dry, roasting: the 35%-KF/MgO-MMT presoma of step 1 preparation is moved in the baking oven, dry 12h under temperature is 80 ℃, grind, sieve through 100 orders, keep sieve sample down, be roasting 4h in 500 ℃ of air atmospheres in temperature at last, namely obtain ternary complex solid base catalyst 35%-KF/MgO-MMT.
Test three: a kind of preparation method of ternary complex solid base catalyst, carry out according to the following steps:
One, preparation 30%-KF/CaO-MMT presoma: 5.0g calcium oxide and 5.0g sodium-based montmorillonite are joined in the reaction bulb that the 10.0mL mass percent concentration is 30% the KF aqueous solution simultaneously, place on the magnetic stirring apparatus and stir, the control mixing speed is 120r/min, place 2h then, obtain the 30%-KF/CaO-MMT presoma;
Two, dry, roasting: the 30%-KF/CaO-MMT presoma of step 1 preparation is moved in the baking oven, dry 12h under temperature is 80 ℃, grind, sieve through 100 orders, keep sieve sample down, be roasting 4h in 500 ℃ of air atmospheres in temperature at last, namely obtain ternary complex solid base catalyst 30%-KF/CaO-MMT.
Test four: a kind of preparation method of ternary complex solid base catalyst, carry out according to the following steps:
One, preparation 50%-KF/CaO-MMT presoma: 5.0g calcium oxide and 5.0g sodium-based montmorillonite are joined in the reaction bulb that the 10.0mL mass percent concentration is 50% the KF aqueous solution simultaneously, place on the magnetic stirring apparatus and stir, the control mixing speed is 120r/min, place 2h then, obtain the 50%-KF/CaO-MMT presoma;
Two, dry, roasting: the 50%-KF/CaO-MMT presoma of step 1 preparation is moved in the baking oven, dry 12h under temperature is 80 ℃, grind, sieve through 100 orders, keep sieve sample down, be roasting 4h in 500 ℃ of air atmospheres in temperature at last, namely obtain ternary complex solid base catalyst 50%-KF/CaO-MMT.
Test five: a kind of preparation method of ternary complex solid base catalyst, carry out according to the following steps:
One, preparation 20%-KF/CaO-MMT presoma: 5.0g calcium oxide and 5.0g sodium-based montmorillonite are joined in the reaction bulb that the 10.0mL mass percent concentration is 20% the KF aqueous solution simultaneously, place on the magnetic stirring apparatus and stir, the control mixing speed is 120r/min, place 2h then, obtain the 20%-KF/CaO-MMT presoma;
Two, dry, roasting: the 20%-KF/CaO-MMT presoma of step 1 preparation is moved in the baking oven, dry 12h under temperature is 80 ℃, grind, sieve through 100 orders, keep sieve sample down, be roasting 4h in 500 ℃ of air atmospheres in temperature at last, namely obtain ternary complex solid base catalyst 20%-KF/CaO-MMT.
Test six: a kind of preparation method of ternary complex solid base catalyst, carry out according to the following steps:
One, preparation 40%-KF/SrO-MMT presoma: 5.0g strontium oxide strontia and 5.0g sodium-based montmorillonite are joined in the reaction bulb that the 10.0mL mass percent concentration is 40% the KF aqueous solution simultaneously, place on the magnetic stirring apparatus and stir, the control mixing speed is 120r/min, place 2h then, obtain the 40%-KF/SrO-MMT presoma;
Two, dry, roasting: the 40%-KF/SrO-MMT presoma of step 1 preparation is moved in the baking oven, dry 12h under temperature is 80 ℃, grind, sieve through 100 orders, keep sieve sample down, be roasting 4h in 500 ℃ of air atmospheres in temperature at last, namely obtain ternary complex solid base catalyst 40%-KF/SrO-MMT.
Test seven: a kind of preparation method of ternary complex solid base catalyst, carry out according to the following steps:
One, preparation 25%-KF/SrO-MMT presoma: 5.0g strontium oxide strontia and 5.0g sodium-based montmorillonite are joined in the reaction bulb that the 10.0mL mass percent concentration is 25% the KF aqueous solution simultaneously, place on the magnetic stirring apparatus and stir, the control mixing speed is 120r/min, place 2h then, obtain the 25%-KF/SrO-MMT presoma;
Two, dry, roasting: the 25%-KF/SrO-MMT presoma of step 1 preparation is moved in the baking oven, dry 12h under temperature is 80 ℃, grind, sieve through 100 orders, keep sieve sample down, be roasting 4h in 500 ℃ of air atmospheres in temperature at last, namely obtain ternary complex solid base catalyst 25%-KF/SrO-MMT.
Test eight: a kind of preparation method of ternary complex solid base catalyst, carry out according to the following steps:
One, preparation 70%-KF/SrO-MMT presoma: 5.0g strontium oxide strontia and 5.0g sodium-based montmorillonite are joined in the reaction bulb that the 10.0mL mass percent concentration is 70% the KF aqueous solution simultaneously, place on the magnetic stirring apparatus and stir, the control mixing speed is 120r/min, place 2h then, obtain the 70%-KF/SrO-MMT presoma;
Two, dry, roasting: the 70%-KF/SrO-MMT presoma of step 1 preparation is moved in the baking oven, dry 12h under temperature is 80 ℃, grind, sieve through 100 orders, keep sieve sample down, be roasting 4h in 500 ℃ of air atmospheres in temperature at last, namely obtain ternary complex solid base catalyst 70%-KF/SrO-MMT.
Test nine: the ternary complex solid base catalyst that utilizes test two to prepare catalyzes and synthesizes the method for new bio diesel oil, carries out according to the following steps:
With 5.0g methyl soyate (0.016mol); 12.2g the 35%-KF/MgO-MMT catalyst of glycol monoethyl ether (0.16mol) and methyl soyate quality 5% joins in the there-necked flask that has condensing reflux; low whipping speed is 250r/min; reaction pressure is normal pressure; nitrogen protection and temperature are 120 ℃ of condition lower magnetic force stirring reaction 6h; be centrifugation 3min under the condition of 1000r/min at rotating speed then; obtaining product is divided into two-layer; separate except sub-cloud 35%-KF/MgO-MMT catalyst; separate the upper strata that obtains and be the new bio diesel fuel mixtures; be that 45 ℃ and vacuum are decompression distillation 0.5h under the condition of 0.1MPa with the new bio diesel fuel mixtures that obtains in temperature at last; the methyl alcohol that separates unreacted glycol monoethyl ether and generation namely obtains new bio diesel oil---soybean oil glycol monoethyl ether ester.
By the FID gas chromatographic analysis, new bio diesel oil---the productive rate of soybean oil glycol monoethyl ether ester can reach 96%.
Test ten: the ternary complex solid base catalyst that utilizes test three to prepare catalyzes and synthesizes the method for new bio diesel oil, carries out according to the following steps:
With 5.0g rapeseed oil fatty acid methyl esters (0.016mol); 19.2g the 30%-KF/CaO-MMT catalyst of diethylene glycol monomethyl ether (0.16mol) and rapeseed oil fatty acid methyl esters quality 5% joins in the there-necked flask that has reflux condensate device; low whipping speed is 250r/min; reaction pressure is normal pressure; nitrogen protection and temperature are 120 ℃ of condition lower magnetic force stirring reaction 6h; be centrifugation 3min under the condition of 1000r/min at rotating speed then; obtaining product is divided into two-layer; separate except sub-cloud 30%-KF/CaO-MMT catalyst; separate the upper strata that obtains and be the new bio diesel fuel mixtures; be that 75 ℃ and vacuum are decompression distillation 1h under the condition of 0.1MPa with the new bio diesel fuel mixtures that obtains in temperature at last; decompression distillation separates the methyl alcohol of unreacted diethylene glycol monomethyl ether and generation, namely obtains new bio diesel oil---rapeseed oil diethylene glycol monomethyl ether ester.
By the FID gas chromatographic analysis, new bio diesel oil---the productive rate of rapeseed oil diethylene glycol monomethyl ether ester can reach 98%.
Test 11: the ternary complex solid base catalyst that utilizes test seven to prepare catalyzes and synthesizes the method for new bio diesel oil, carries out according to the following steps:
With 5.0g methyl laurate (0.023mol); 9.6g the 25%-KF/SrO-MMT catalyst of triethylene glycol monomethyl ether (0.046mol) and methyl laurate quality 5% joins in the there-necked flask that has reflux condensate device; low whipping speed is 250r/min; reaction pressure is normal pressure; nitrogen protection and temperature are 120 ℃ of condition lower magnetic force stirring reaction 6h; be centrifugation 3min under the condition of 1000r/min at rotating speed then; obtaining product is divided into two-layer; separate except sub-cloud 25%-KF/SrO-MMT catalyst; separate the upper strata that obtains and be the new bio diesel fuel mixtures; be that 100 ℃ and vacuum are decompression distillation 1.5h under the condition of 0.1MPa with the new bio diesel fuel mixtures that obtains in temperature at last; decompression distillation separates the methyl alcohol of unreacted triethylene glycol monomethyl ether and generation, namely obtains new bio diesel oil---laurate triethylene glycol monomethyl ether ester.
By the FID gas chromatographic analysis, new bio diesel oil---the productive rate of laurate triethylene glycol monomethyl ether ester can reach 99%.
Existing catalyst contrast test:
Test nine control group: be raw material synthesizing new method of bio-diesel oil with methyl soyate and glycol monoethyl ether, carry out according to the following steps:
One, the preparation of potassium alkoxide solution: in the 100mL conical flask, add 12.2g glycol monoethyl ether and 0.04g potassium hydroxide successively, mix to shake to potassium hydroxide and dissolve fully, obtain potassium alkoxide solution;
Two; ester exchange reaction: 5.0g methyl soyate (0.016mol) is joined in the there-necked flask that has condensing reflux; nitrogen protection; constant temperature after water-bath is heated to 60 ℃; the potassium alkoxide solution (being heated to 60 ℃) that adds the step 1 preparation under the vigorous stirring; reaction 2h; product cooling back moves in the 1000mL separatory funnel; add the neutralization of 10% dilute hydrochloric acid solution; be neutral to solution; separate and remove lower floor's water; upper solution is washed 3 times with saturated NaCl solution (150mL); separate, remove lower floor's water, the upper solution decompression distillation separates the methyl alcohol of unreacted glycol monoethyl ether and generation; drying gets new bio diesel oil---soybean oil glycol monoethyl ether ester.
By the FID gas chromatographic analysis, the productive rate of new bio diesel oil---soybean oil glycol monoethyl ether ester is 83%.
Test 11 control group: with methyl laurate and triethylene glycol monomethyl ether be raw material synthetic two generation method of bio-diesel oil, carry out according to the following steps:
One, the preparation of pure sodium solution: in the 100mL conical flask, add 12.2g glycol monoethyl ether and 0.025g sodium successively, till liquid level no longer includes unsteady sodium, obtain pure sodium solution;
Two, ester exchange reaction: with 5.0g methyl laurate (0.023mol), join in the there-necked flask that has reflux condensate device, constant temperature after water-bath is heated to 90 ℃, the pure sodium solution (being heated to 90 ℃) that adds the step 1 preparation under the vigorous stirring, reaction 2h, product moves in the 1000mL separatory funnel, add the neutralization of 10% dilute hydrochloric acid solution, be neutral to solution, separate and remove lower floor's water, the upper strata is washed 3 times with saturated NaCl solution (150mL), separatory is removed lower floor's water, and the methyl alcohol of unreacted glycol monoethyl ether and generation, drying are reclaimed in the upper solution decompression distillation, get faint yellow clear product, i.e. new bio diesel oil---laurate triethylene glycol monomethyl ether ester.
By the FID gas chromatographic analysis, the productive rate of new bio diesel oil---laurate triethylene glycol monomethyl ether ester is 81%.
Claims (9)
1. the preparation method of a ternary complex solid base catalyst, the preparation method who it is characterized in that ternary complex solid base catalyst carries out according to the following steps:
One, preparation x-KF/MO-MMT presoma: be that to join mass percent concentration at 1: 1 be to stir in 5%～70% the KF aqueous solution by mass ratio with alkaline earth oxide and sodium-based montmorillonite, the control mixing speed is 100r/min～120r/min, place 2h then, obtain the x-KF/MO-MMT presoma; The gross mass of described alkaline earth oxide and sodium-based montmorillonite and mass percent concentration are that the volume ratio of 5%～70% the KF aqueous solution is 1g: 1mL;
Two, dry, roasting: the x-KF/MO-MMT presoma of step 1 preparation is moved in the baking oven, dry 12h under temperature is 80 ℃, grind, sieve through 100 orders, keep sieve sample down, be roasting 4h in 400 ℃～600 ℃ air atmospheres in temperature at last, namely obtain ternary complex solid base catalyst x-KF/MO-MMT.
2. the preparation method of a kind of ternary complex solid base catalyst according to claim 1 is characterized in that the alkaline earth oxide described in the step 1 is magnesia, calcium oxide, strontium oxide strontia or barium monoxide.
3. the preparation method of a kind of ternary complex solid base catalyst according to claim 1, the mass percent concentration that it is characterized in that the KF aqueous solution described in the step 1 is 5%.
4. the preparation method of a kind of ternary complex solid base catalyst according to claim 1, the mass percent concentration that it is characterized in that the KF aqueous solution described in the step 1 is 20%.
5. the preparation method of a kind of ternary complex solid base catalyst according to claim 1, the mass percent concentration that it is characterized in that the KF aqueous solution described in the step 1 is 30%.
6. the preparation method of a kind of ternary complex solid base catalyst according to claim 1, the mass percent concentration that it is characterized in that the KF aqueous solution described in the step 1 is 70%.
7. the ternary complex solid base catalyst that utilizes preparation method as claimed in claim 1 to prepare catalyzes and synthesizes the method for new bio diesel oil, it is characterized in that the method for utilizing ternary complex solid base catalyst to catalyze and synthesize new bio diesel oil is to carry out according to the following steps:
With fatty acid methyl ester, poly glycol monomethyl ether and ternary complex solid base catalyst add in the reactor of taking back the stream condensing unit, low whipping speed is 250r/min, reaction pressure is normal pressure, nitrogen protection and temperature are 60 ℃～150 ℃ condition lower magnetic force stirring reaction 2h～10h, be centrifugation 3min～5min under the condition of 800r/min～1000r/min at rotating speed then, obtaining product is divided into two-layer, separate the upper strata that obtains and be the new bio diesel fuel mixtures, be that 45 ℃～145 ℃ and vacuum are decompression distillation 0.5h～3h under the condition of 0.1MPa with the new bio diesel fuel mixtures that obtains in temperature at last, namely obtain new bio diesel oil; The mol ratio of described poly glycol monomethyl ether and fatty acid methyl ester is (1～20): 1, and the mass ratio of described ternary complex solid base catalyst and fatty acid methyl ester is (0.1～10): 100.
8. the method for utilizing ternary complex solid base catalyst to catalyze and synthesize new bio diesel oil according to claim 7 is characterized in that described fatty acid methyl ester is a kind of in methyl caprylate, methyl caprate, methyl laurate, myristic acid methyl esters, methyl hexadecanoate, methyl stearate, methyl oleate, methyl linoleate, methyl linolenate, methyl soyate and the rapeseed oil fatty acid methyl esters or several mixture wherein.
9. the method for utilizing ternary complex solid base catalyst to catalyze and synthesize new bio diesel oil according to claim 7 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 1,2,3,4,5,7,9,10,15 or 20.
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| CN104226346A (en) * | 2014-09-28 | 2014-12-24 | 佛山市天晟隆油脂化工有限公司 | Preparation method for solid base catalyst |
| CN104226343A (en) * | 2014-09-28 | 2014-12-24 | 佛山市天晟隆油脂化工有限公司 | Preparation method for solid base catalyst |
| CN104258882A (en) * | 2014-09-28 | 2015-01-07 | 佛山市天晟隆油脂化工有限公司 | Preparation method of solid base catalyst |
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| CN104226346A (en) * | 2014-09-28 | 2014-12-24 | 佛山市天晟隆油脂化工有限公司 | Preparation method for solid base catalyst |
| CN104226343A (en) * | 2014-09-28 | 2014-12-24 | 佛山市天晟隆油脂化工有限公司 | Preparation method for solid base catalyst |
| CN104258882A (en) * | 2014-09-28 | 2015-01-07 | 佛山市天晟隆油脂化工有限公司 | Preparation method of solid base catalyst |
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