CN103406118A - Bio-diesel catalyst CaO/M-Al-O and preparation method thereof - Google Patents
Bio-diesel catalyst CaO/M-Al-O and preparation method thereof Download PDFInfo
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- CN103406118A CN103406118A CN2013103606339A CN201310360633A CN103406118A CN 103406118 A CN103406118 A CN 103406118A CN 2013103606339 A CN2013103606339 A CN 2013103606339A CN 201310360633 A CN201310360633 A CN 201310360633A CN 103406118 A CN103406118 A CN 103406118A
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Abstract
The invention relates to technologies of solid catalyst preparation and bio-diesel synthesis, in particular relates to a bio-diesel catalyst, and specifically relates to a bio-diesel catalyst CaO/M-Al-O and a preparation method thereof. In order to obtain highly dispersed CaO-loaded solid base by sufficiently utilizing an active component CaO, and in order to apply the solid base to the synthesis of bio-diesel, the invention provides a CaO/M-Al-O solid base as well as a preparation method and application thereof to synthesis of bio-diesel. According to the technical scheme adopted in the invention, the CaO/M-Al-O solid base is provided; the active component CaO is highly dispersed onto supported type solid base formed on an M-Al-O composite oxide carrier with a specific surface area of 150 m<2>/g-250m<2>/g, pore volume of 0.5 cm<3>/g-1.0cm<3>/g in a mass ratio m(CaO)/m(CaO/M-Al-O) of 0.06-0.12, wherein M is Mg or Zn.
Description
Technical field
The present invention relates to solid catalyst preparation and biodiesel synthesis technical field, particularly biodiesel catalyst, be specially a kind of biodiesel catalyst CaO/M-Al-O and preparation method thereof.
Background technology
CaO is because its raw material sources are abundant, cheap, alkalescence strong, and the solubility in methyl alcohol is little, recovery is easy, is widely studied and applies as the biodiesel heterogeneous catalysis.The calcium methoxide that CaO and methyl alcohol effect generate is the active component of current grease alcoholysis biodiesel synthesis of generally acknowledging, calcium methoxide is insoluble to methyl alcohol, in reaction system, exist with the suspension colloid state, have larger active surface, present stronger alkalescence and higher catalytic activity.CaO is used alone as biodiesel catalyst and has following shortcoming: specific area is less, and the Adsorption that unit mass provides is less, and the utilization rate of catalyst is lower; The reaction that saponification side reaction and catalyst and glycerine generate glycerine calcium easily occurs, cause catalyst and amounts of glycerol to reduce, sticky shape material increases, and causes catalyst and glycerine separation difficulty; In addition, catalyst has oligodynamical to run off in reactant liquor, makes the biodiesel product show certain alkalescence.
For the advantage that takes full advantage of the CaO solid base, the shortcoming existed while avoiding using separately, the researcher CaO load on specific area, pore volume, aperture all larger and easily and CaO form on the carrier of pretending use and prepared a series of load type solid body base catalysts, as CaO/SiO
2, CaO/ γ-Al
2O
3, CaO/MgO, CaO-ZrO
2, CaO/ZnO, CaO/MCM-41, CaO/ SBA-15 etc.The CaO that these catalyst merchandisers are solely used compares, and the utilization rate of active component CaO has improved, and loss by dissolution has reduced, and mostly shows stronger antiacid, water resistant and the ability of anti-saponification and good repeat performance.
Summary of the invention
The purpose of this invention is to provide a kind of new load type solid body base catalyst, i.e. biodiesel catalyst CaO/M-Al-O.
The present invention adopts following technical scheme to realize:
A kind of biodiesel catalyst CaO/M-Al-O, comprise active component CaO and composite oxides M-Al-O, the mass ratio of described active component CaO and catalyst CaO/M-Al-O
m(CaO)/
m(CaO/M-Al-O)=0.06～0.12; Wherein, M=Mg or Zn.
Above-mentioned biodiesel catalyst CaO/M-Al-O, because specific area, pore volume and the aperture of the composite oxides after the roasting of magnalium (or zinc-aluminium) hydrotalcite are all larger, therefore active component CaO is loaded on its composite oxides surface, can take full advantage of active component CaO, reduce the loss by dissolution of active component CaO in reactant liquor, reduce side reaction, improve the separating effect of catalyst and by-product glycerin.Active component CaO loads on the catalyst for preparing on magnalium (or zinc-aluminium) hydrotalcite product of roasting surface in the application of catalytically synthesizing biological diesel oil, has obtained effect preferably.
The preparation method of above-mentioned biodiesel catalyst CaO/M-Al-O is as follows:
(1), with reference to natural magnesium aluminum hydrotalcite molecular formula Mg
6Al
2(OH)
16CO
34H
2Element proportioning in O, in molar ratio
n(M):
n(Al):
n(OH
-):
n(CO
3 2-)=6:2:16:1～5, get 6 parts of M (NO
3)
26H
2O and 2 parts of Al (NO
3)
39H
2O, be made into water solution A; Get 16 parts of NaOH and 1～5 part of Na
2CO
3, be made into aqueous solution B;
(2), adopt and addition, water solution A and aqueous solution B are mixed and make it that coprecipitation reaction occur, through ageing, filtration, washing, drying, obtain the M-Al hydrotalcite;
(3), adopt the excess solution infusion process, with mass fraction, be 0.15～0.25 Ca (Ac)
2(calcium acetate) aqueous solution dipping M-Al hydrotalcite, flood 10h～15h under 20 ℃～25 ℃, then filter, be drying to obtain Ca (Ac)
2/ M-Al hydrotalcite;
(4), at the temperature of 700 ℃～900 ℃, by Ca (Ac)
2/ M-Al hydrotalcite roasting 1h～5h, obtain biodiesel catalyst CaO/M-Al-O.
Preferably, by described active component CaO high degree of dispersion in specific area at 150 m
2/ g～250m
2/ g, pore volume are at 0.5cm
3/ g～1.0cm
3/ g, average pore radius are in 5nm～12nm, mol ratio
n(M):
n(Al):
n(O) on the M-Al-O composite oxide carrier of=3:1:4.5, the catalytic effect carried out is better.
It is as follows that biodiesel catalyst CaO/M-Al-O of the present invention is applied to catalytically synthesizing biological diesel oil:
In there-necked flask, react, the control reaction condition is: mol ratio
n(alcohol)/
n(oil)=6～12, mass ratio
m(catalyst)/
m(oil)=0.03～0.08, stir speed (S.S.) 400r/min～600 r/min, 55 ℃～65 ℃ of reaction temperatures, reaction time 3h～6h.Reaction is cooled to room temperature by reactant liquor after finishing, and pours centrifuge tube into, and the setting centrifuge speed is 6000r/min, and the time is 5min, and catalyst is removed in centrifugation.
Reactant liquor after the removal catalyst is poured in there-necked flask, and methyl alcohol is removed in air-distillation, and liquidus temperature is controlled at 140 ℃.After methyl alcohol has steamed, raffinate is cooled to room temperature, pour centrifuge tube into, setting centrifuge speed is 5min, centrifugation again in 10000r/min, time.The reactant liquor of centrifugal layering is poured in separatory funnel, emitted after lower floor's glycerine that namely to obtain viscosity little, of light color, be almost neutral biodiesel product.
Compared with prior art, the advantage of technical solution of the present invention is: active component CaO high degree of dispersion is in specific area, pore volume and aperture all on larger magnalium (or zinc-aluminium) hydrotalcite product of roasting surface, the utilization rate of active component CaO is high, loss by dissolution is few, and catalyst separates easily with glycerin by-products.
The present invention is reasonable in design, and active component CaO loads on the catalyst for preparing on magnalium (or zinc-aluminium) hydrotalcite product of roasting surface and the application in catalytically synthesizing biological diesel oil thereof, has not yet to see report.
The accompanying drawing explanation
Fig. 1 is the Ca (Ac) made
2The TG-DTA figure of/Mg-Al hydrotalcite, as can be seen from Figure 1, Ca (Ac)
2/ Mg-Al hydrotalcite has 2 obvious weightless ladders in heating process: the ladder between 350 ℃～450 ℃ is by Ca (Ac)
2Be decomposed into CaCO
3And acetone, de-OH on Mg-Al hydrotalcite layer
-Generate H
2O, the de-CO of interlayer
3 2-Generate CO
2Institute causes, corresponding 1 the obvious exothermic peak of this warm area.Ladder between 760 ℃～810 ℃ is by CaCO
3Be decomposed into CaO and CO
2Institute causes, corresponding 1 the obvious endothermic peak of this warm area.
Fig. 2 is the XRD spectra of the CaO/Mg-Al-O that makes, and as seen from Figure 2, the spectrum peak is not only wide but also short steamed bun peak, shows non-crystal feature, and catalyst consists of the crystallite of fine particle.Do not show MgO, Al
2O
3, the CaO crystal characteristic diffraction peak, infer that magnalium exists with the microcrystalline form of composite oxides, active component CaO with amorphous or crystallite form high degree of dispersion in the Mg-Al composite oxide surface.
Fig. 3 is the SEM figure of the CaO/Mg-Al-O that makes, and as seen from Figure 3, CaO/Mg-Al-O solid base catalyst surface topography is irregular cellular, and depression and projection size are between 2～10 μ m.
Fig. 4 is the Ca (Ac) made
2The TG-DTA figure of/Zn-Al hydrotalcite, as can be seen from Figure 4, Ca (Ac)
2/ Zn-Al hydrotalcite has 3 obvious weightless ladders in heating process: the ladder between 150 ℃～270 ℃ is by Zn-Al hydrotalcite surface physics adsorbed water and interlayer chemically combined water of crystallization, to lose institute to cause, corresponding 1 the obvious endothermic peak of this warm area.Ladder between 380 ℃～450 ℃ is by Ca (Ac)
2Be decomposed into CaCO
3And acetone, de-OH on Zn-Al hydrotalcite layer
-Generate H
2O, the de-CO of interlayer
3 2-Generate CO
2Institute causes, corresponding 1 the obvious exothermic peak of this warm area.Ladder between 740 ℃～800 ℃ is by CaCO
3Be decomposed into CaO and CO
2Institute causes, corresponding 1 the obvious endothermic peak of this warm area.
Fig. 5 is the XRD spectra of the CaO/Zn-Al-O that makes, and as seen from Figure 5, this spectrogram is shown as the characteristic diffraction peak of six side's ZnO crystals, does not show Al
2O
3The characteristic diffraction peak of crystal, show that the Al atom penetrates in six side ZnO lattices.The characteristic diffraction peak that does not show the CaO crystal, show active component CaO with amorphous or crystallite form high degree of dispersion in carrier surface.
Fig. 6 is the SEM figure of the CaO/Zn-Al-O that makes, and as seen from Figure 6, CaO/Zn-Al-O solid base catalyst surface topography is irregular cellular, and depression and projection size are between 2 μ m～10 μ m.
The specific embodiment
Below specific embodiments of the invention are elaborated.
A kind of biodiesel catalyst CaO/Mg-Al-O, comprise active component CaO and composite oxides Mg-Al-O, the mass ratio of described active component CaO and catalyst CaO/Mg-Al-O
m(CaO)/
m(CaO/Mg-Al-O)=0.12.
The preparation method of CaO/Mg-Al-O solid base is as follows:
(1), in molar ratio
n(Mg):
n(Al):
n(OH
-):
n(CO
3 2-)=6:2:16:1, take 16.15g Mg (NO
3)
26H
2O(0.063mol) and 7.88g Al (NO
3)
39H
2O(0.021mol), put into the 250mL conical flask, add the 50mL deionized water dissolving to obtain water solution A; Take 6.72g NaOH(0.168mol) and 1.11g Na
2CO
3(0.0105mol), put into another 250mL conical flask, add the 50mL deionized water dissolving to obtain aqueous solution B.
(2), water solution A and aqueous solution B are respectively charged in two constant pressure funnels, in the 500mL four-hole boiling flask, first put into the 50mL deionized water, turn on agitator, regulate two constant pressure funnels, make water solution A and aqueous solution B be added drop-wise in four-hole boiling flask and form mixed solution with certain speed.Regulate at any time and drip the fast pH value stabilization that makes mixed solution between 9～10, it is 1.25mL/min that the control water solution A splashes into speed, and precipitation reaction temperature is 42 ℃.After solution A dropwises, stop splashing into solution B, continue to stir 30 min.Reactant liquor is poured in conical flask, covered stopper, put into thermostat, 90 ℃ of lower ageings 48 hours, then filter, wash, until the pH value of filtrate is about 7, filter cake is put into to vacuum drying chamber, dry 24h under 60 ℃, obtain the Mg-Al hydrotalcite.
(3), in mass ratio
m(calcium acetate solution)/
m(Mg-Al hydrotalcite)=5, flood the Mg-Al hydrotalcite with the calcium acetate solution that mass fraction is 0.25, and dipping 14 h, then filter under 20 ℃, and filter cake is put into to vacuum drying chamber, and dry 4h under 100 ℃, obtain Ca (Ac)
2/ Mg-Al hydrotalcite.
(4), by Ca (Ac)
2/ Mg-Al hydrotalcite is placed in crucible puts into Muffle furnace, at 800 ℃ of lower roasting 2h, obtains the CaO/Mg-Al-O solid base catalyst.
Above-mentioned CaO/Mg-Al-O catalyzed by solid base biodiesel synthesis is as follows:
Take 3g CaO/Mg-Al-O solid base, put into the 250mL there-necked flask, add 38mL methyl alcohol, add hot reflux 30 min, then add the 100mL rapeseed oil that is preheating to 65 ℃, the adjusting stir speed (S.S.) is 400r/min, reacts 4h under 65 ℃.Reactant liquor is cooled to room temperature, pours centrifuge tube into, the setting centrifuge speed is 6000r/min, and the time is 6min, and catalyst is removed in centrifugation.
Reactant liquor after the removal catalyst is poured in there-necked flask, and methyl alcohol is removed in air-distillation, and liquidus temperature is controlled at 140 ℃.After methyl alcohol has steamed, raffinate is cooled to room temperature, pour centrifuge tube into, the setting centrifuge speed is that 10000r/min, time are 6min, centrifugation again.The reactant liquor of centrifugal layering is poured in separatory funnel, namely obtained the biodiesel product after emitting lower floor's glycerine, the rapeseed oil conversion ratio is 98.4%.
A kind of biodiesel catalyst CaO/Mg-Al-O, comprise active component CaO and composite oxides Mg-Al-O, the mass ratio of described active component CaO and catalyst CaO/Mg-Al-O
m(CaO)/
m(CaO/Mg-Al-O)=0.09.
The preparation method of CaO/Mg-Al-O solid base is as follows:
(1), in molar ratio
n(Mg):
n(Al):
n(OH
-):
n(CO
3 2-)=6:2:16:3, take 16.15g Mg (NO
3)
26H
2O(0.063mol) and 7.88g Al (NO
3)
39H
2O(0.021mol), put into the 250mL conical flask, add the 50mL deionized water dissolving to obtain water solution A; Take 6.72g NaOH(0.168mol) and 3.34g Na
2CO
3(0.0315mol), put into another 250mL conical flask, add the 50mL deionized water dissolving to obtain aqueous solution B.
(2), water solution A and aqueous solution B are respectively charged in two constant pressure funnels, in the 500mL four-hole boiling flask, first put into the 50mL deionized water, turn on agitator, regulate two constant pressure funnels, make water solution A and aqueous solution B be added drop-wise in four-hole boiling flask and form mixed solution with certain speed.Regulate at any time and drip the fast pH value stabilization that makes mixed solution between 9～10, it is 1.0mL/min that the control water solution A splashes into speed, and precipitation reaction temperature is 40 ℃.After solution A dropwises, stop splashing into solution B, continue to stir 30 min.Reactant liquor is poured in conical flask, covered stopper, put into thermostat, 90 ℃ of lower ageings 48 hours, then filter, wash, until the pH value of filtrate is about 7, filter cake is put into to vacuum drying chamber, dry 24h under 60 ℃, obtain the Mg-Al hydrotalcite.
(3), in mass ratio
m(calcium acetate solution)/
m(Mg-Al hydrotalcite)=5, flood the Mg-Al hydrotalcite with the calcium acetate solution that mass fraction is 0.2, and dipping 14 h, then filter under 20 ℃, and filter cake is put into to vacuum drying chamber, and dry 4h under 100 ℃, obtain Ca (Ac)
2/ Mg-Al hydrotalcite.
(4), by Ca (Ac)
2/ Mg-Al hydrotalcite is placed in crucible puts into Muffle furnace, at 900 ℃ of lower roasting 1h, obtains the CaO/Mg-Al-O solid base catalyst.
Above-mentioned CaO/Mg-Al-O catalyzed by solid base biodiesel synthesis is as follows:
Take 3g CaO/Mg-Al-O solid base, put into the 250mL there-necked flask, add 38mL methyl alcohol, add hot reflux 30 min, then add the 100mL rapeseed oil that is preheating to 65 ℃, the adjusting stir speed (S.S.) is 400r/min, reacts 4h under 65 ℃.Reactant liquor is cooled to room temperature, pours centrifuge tube into, the setting centrifuge speed is 6000r/min, and the time is 6min, and catalyst is removed in centrifugation.
Reactant liquor after the removal catalyst is poured in there-necked flask, and methyl alcohol is removed in air-distillation, and liquidus temperature is controlled at 140 ℃.After methyl alcohol has steamed, raffinate is cooled to room temperature, pour centrifuge tube into, the setting centrifuge speed is that 10000r/min, time are 6min, centrifugation again.The reactant liquor of centrifugal layering is poured in separatory funnel, namely obtained the biodiesel product after emitting lower floor's glycerine, the rapeseed oil conversion ratio is 96.5%.
Embodiment 3
A kind of biodiesel catalyst CaO/Mg-Al-O, comprise active component CaO and composite oxides Mg-Al-O, the mass ratio of described active component CaO and catalyst CaO/Mg-Al-O
m(CaO)/
m(CaO/Mg-Al-O)=0.06.
The preparation method of CaO/Mg-Al-O solid base is as follows:
(1), in molar ratio
n(Mg):
n(Al):
n(OH
-):
n(CO
3 2-)=6:2:16:5, take 16.15g Mg (NO
3)
26H
2O(0.063mol) and 7.88g Al (NO
3)
39H
2O(0.021mol), put into the 250mL conical flask, add the 50mL deionized water dissolving to obtain water solution A; Take 6.72g NaOH(0.168mol) and 5.56g Na
2CO
3(0.0525mol), put into another 250mL conical flask, add the 75mL deionized water dissolving to obtain aqueous solution B.
(2), water solution A and aqueous solution B are respectively charged in two constant pressure funnels, in the 500mL four-hole boiling flask, first put into the 50mL deionized water, turn on agitator, regulate two constant pressure funnels, make water solution A and aqueous solution B be added drop-wise in four-hole boiling flask and form mixed solution with certain speed.Regulate at any time and drip the fast pH value stabilization that makes mixed solution between 9～10, it is 1.5mL/min that the control water solution A splashes into speed, and precipitation reaction temperature is 38 ℃.After solution A dropwises, stop splashing into solution B, continue to stir 30 min.Reactant liquor is poured in conical flask, covered stopper, put into thermostat, 90 ℃ of lower ageings 48 hours, then filter, wash, until the pH value of filtrate is about 7, filter cake is put into to vacuum drying chamber, dry 24h under 60 ℃, obtain the Mg-Al hydrotalcite.
(3), in mass ratio
m(calcium acetate solution)/
m(Mg-Al hydrotalcite)=5, flood the Mg-Al hydrotalcite with the calcium acetate solution that mass fraction is 0.15, and dipping 14 h, then filter under 20 ℃, and filter cake is put into to vacuum drying chamber, and dry 4h under 100 ℃, obtain Ca (Ac)
2/ Mg-Al hydrotalcite.
(4), by Ca (Ac)
2/ Mg-Al hydrotalcite is placed in crucible puts into Muffle furnace, at 700 ℃ of lower roasting 5h, obtains the CaO/Mg-Al-O solid base catalyst.
Above-mentioned CaO/Mg-Al-O catalyzed by solid base biodiesel synthesis is as follows:
Take 3g CaO/Mg-Al-O solid base, put into the 250mL there-necked flask, add 38mL methyl alcohol, add hot reflux 30 min, then add the 100mL rapeseed oil that is preheating to 65 ℃, the adjusting stir speed (S.S.) is 400r/min, reacts 4h under 65 ℃.Reactant liquor is cooled to room temperature, pours centrifuge tube into, the setting centrifuge speed is 6000r/min, and the time is 6min, and catalyst is removed in centrifugation.
Reactant liquor after the removal catalyst is poured in there-necked flask, and methyl alcohol is removed in air-distillation, and liquidus temperature is controlled at 140 ℃.After methyl alcohol has steamed, raffinate is cooled to room temperature, pour centrifuge tube into, the setting centrifuge speed is that 10000r/min, time are 6min, centrifugation again.The reactant liquor of centrifugal layering is poured in separatory funnel, namely obtained the biodiesel product after emitting lower floor's glycerine, the rapeseed oil conversion ratio is 97.2%.
A kind of biodiesel catalyst CaO/Zn-Al-O, comprise active component CaO and composite oxides Zn-Al-O, the mass ratio of described active component CaO and catalyst CaO/Zn-Al-O
m(CaO)/
m(CaO/Zn-Al-O)=0.12.
Synthesizing of above-mentioned CaO/Zn-Al-O solid base:
(1), in molar ratio
n(Zn):
n(Al):
n(OH
-):
n(CO
3 2-)=6:2:16:1, take 17.85g Zn (NO
3)
26H
2O(0.060mol) and 7.50g Al (NO
3)
39H
2O(0.020mol), put into the 250mL conical flask, add the 75mL deionized water dissolving to obtain water solution A; Take 6.40g NaOH(0.160mol) and 1.06g Na
2CO
3(0.010mol), put into another 250mL conical flask, add the 50mL deionized water dissolving to obtain aqueous solution B.
(2), water solution A and aqueous solution B are respectively charged in two constant pressure funnels, in the 500mL four-hole boiling flask, first put into the 50mL deionized water, turn on agitator, regulate two constant pressure funnels, make water solution A and aqueous solution B be added drop-wise in four-hole boiling flask and form mixed solution with certain speed.Regulate at any time and drip the fast pH value stabilization that makes mixed solution between 9～10, it is 1.5mL/min that the control water solution A splashes into speed, and precipitation reaction temperature is 60 ℃.After solution A dropwises, stop splashing into solution B, continue to stir 30 min.Reactant liquor is poured in conical flask, covered stopper, put into thermostat, 90 ℃ of lower ageings 48 hours, then filter, wash, until the pH value of filtrate is about 7, filter cake is put into to vacuum drying chamber, dry 24h under 60 ℃, obtain the Zn-Al hydrotalcite.
(3), in mass ratio
m(calcium acetate solution)/
m(Zn-Al hydrotalcite)=5, flood the Zn-Al hydrotalcite with the calcium acetate solution that mass fraction is 0.25, and dipping 13 h, then filter under 20 ℃, and filter cake is put into to vacuum drying chamber, and dry 1h under 100 ℃, obtain Ca (Ac)
2/ Zn-Al hydrotalcite.
(4), by Ca (Ac)
2/ Zn-Al hydrotalcite is placed in crucible puts into Muffle furnace, and roasting 3 h, obtain the CaO/Zn-Al-O solid base catalyst under 750 ° of C.
Above-mentioned CaO/Zn-Al-O catalyzed by solid base biodiesel synthesis is as follows:
Take 3g CaO/Zn-Al-O solid base, put into the 250mL there-necked flask, add 38mL methyl alcohol, add hot reflux 30min, then add the 100mL rapeseed oil that is preheating to 65 ℃, the adjusting stir speed (S.S.) is 400r/min, reacts 4h under 65 ℃.Reactant liquor is cooled to room temperature, pours centrifuge tube into, the setting centrifuge speed is 6000r/min, and the time is 6min, and catalyst is removed in centrifugation.
Reactant liquor after the removal catalyst is poured in there-necked flask, and methyl alcohol is removed in air-distillation, and liquidus temperature is controlled at 140 ℃.After methyl alcohol has steamed, raffinate is cooled to room temperature, pour centrifuge tube into, the setting centrifuge speed is that 10000r/min, time are 6min, centrifugation again.The reactant liquor of centrifugal layering is poured in separatory funnel, namely obtained the biodiesel product after emitting lower floor's glycerine, the rapeseed oil conversion ratio is 96.0%.
A kind of biodiesel catalyst CaO/Zn-Al-O, comprise active component CaO and composite oxides Zn-Al-O, the mass ratio of described active component CaO and catalyst CaO/Zn-Al-O
m(CaO)/
m(CaO/Zn-Al-O)=0.09.
Synthesizing of above-mentioned CaO/Zn-Al-O solid base:
(1), in molar ratio
n(Zn):
n(Al):
n(OH
-):
n(CO
3 2-)=6:2:16:3, take 17.85g Zn (NO
3)
26H
2O(0.060mol) and 7.50g Al (NO
3)
39H
2O(0.020mol), put into the 250mL conical flask, add the 75mL deionized water dissolving to obtain water solution A; Take 6.40g NaOH(0.160mol) and 3.18g Na
2CO
3(0.030mol), put into another 250mL conical flask, add the 50mL deionized water dissolving to obtain aqueous solution B.
(2), water solution A and aqueous solution B are respectively charged in two constant pressure funnels, in the 500mL four-hole boiling flask, first put into the 50mL deionized water, turn on agitator, regulate two constant pressure funnels, make water solution A and aqueous solution B be added drop-wise in four-hole boiling flask and form mixed solution with certain speed.Regulate at any time and drip the fast pH value stabilization that makes mixed solution between 9～10, it is 1.25mL/min that the control water solution A splashes into speed, and precipitation reaction temperature is 62 ℃.After solution A dropwises, stop splashing into solution B, continue to stir 30 min.Reactant liquor is poured in conical flask, covered stopper, put into thermostat, 90 ℃ of lower ageings 48 hours, then filter, wash, until the pH value of filtrate is about 7, filter cake is put into to vacuum drying chamber, dry 24h under 60 ℃, obtain the Zn-Al hydrotalcite.
(3), in mass ratio
m(calcium acetate solution)/
m(Zn-Al hydrotalcite)=5, flood the Zn-Al hydrotalcite with the calcium acetate solution that mass fraction is 0.20, and dipping 13 h, then filter under 20 ℃, and filter cake is put into to vacuum drying chamber, and dry 1h under 100 ℃, obtain Ca (Ac)
2/ Zn-Al hydrotalcite.
(4), by Ca (Ac)
2/ Zn-Al hydrotalcite is placed in crucible puts into Muffle furnace, and roasting 4 h, obtain the CaO/Zn-Al-O solid base catalyst under 700 ° of C.
Above-mentioned CaO/Zn-Al-O catalyzed by solid base biodiesel synthesis is as follows:
Take 3g CaO/Zn-Al-O solid base, put into the 250mL there-necked flask, add 38mL methyl alcohol, add hot reflux 30min, then add the 100mL rapeseed oil that is preheating to 65 ℃, the adjusting stir speed (S.S.) is 400r/min, reacts 4h under 65 ℃.Reactant liquor is cooled to room temperature, pours centrifuge tube into, the setting centrifuge speed is 6000r/min, and the time is 6min, and catalyst is removed in centrifugation.
Reactant liquor after the removal catalyst is poured in there-necked flask, and methyl alcohol is removed in air-distillation, and liquidus temperature is controlled at 140 ℃.After methyl alcohol has steamed, raffinate is cooled to room temperature, pour centrifuge tube into, the setting centrifuge speed is that 10000r/min, time are 6min, centrifugation again.The reactant liquor of centrifugal layering is poured in separatory funnel, namely obtained the biodiesel product after emitting lower floor's glycerine, the rapeseed oil conversion ratio is 95.1%.
A kind of biodiesel catalyst CaO/Zn-Al-O, comprise active component CaO and composite oxides Zn-Al-O, the mass ratio of described active component CaO and catalyst CaO/Zn-Al-O
m(CaO)/
m(CaO/Zn-Al-O)=0.06.
Synthesizing of above-mentioned CaO/Zn-Al-O solid base:
(1), in molar ratio
n(Zn):
n(Al):
n(OH
-):
n(CO
3 2-)=6:2:16:5, take 17.85g Zn (NO
3)
26H
2O(0.060mol) and 7.50g Al (NO
3)
39H
2O(0.020mol), put into the 250mL conical flask, add the 75mL deionized water dissolving to obtain water solution A; Take 6.40g NaOH(0.160mol) and 5.30g Na
2CO
3(0.050mol), put into another 250mL conical flask, add the 50mL deionized water dissolving to obtain aqueous solution B.
(2), water solution A and aqueous solution B are respectively charged in two constant pressure funnels, in the 500mL four-hole boiling flask, first put into the 50mL deionized water, turn on agitator, regulate two constant pressure funnels, make water solution A and aqueous solution B be added drop-wise in four-hole boiling flask and form mixed solution with certain speed.Regulate at any time and drip the fast pH value stabilization that makes mixed solution between 9～10, it is 1.0mL/min that the control water solution A splashes into speed, and precipitation reaction temperature is 58 ℃.After solution A dropwises, stop splashing into solution B, continue to stir 30 min.Reactant liquor is poured in conical flask, covered stopper, put into thermostat, 90 ℃ of lower ageings 48 hours, then filter, wash, until the pH value of filtrate is about 7, filter cake is put into to vacuum drying chamber, dry 24h under 60 ℃, obtain the Zn-Al hydrotalcite.
(3), in mass ratio
m(calcium acetate solution)/
m(Zn-Al hydrotalcite)=5, flood the Zn-Al hydrotalcite with the calcium acetate solution that mass fraction is 0.15, and dipping 13 h, then filter under 20 ℃, and filter cake is put into to vacuum drying chamber, and dry 1h under 100 ℃, obtain Ca (Ac)
2/ Zn-Al hydrotalcite.
(4), by Ca (Ac)
2/ Zn-Al hydrotalcite is placed in crucible puts into Muffle furnace, and roasting 2 h, obtain the CaO/Zn-Al-O solid base catalyst under 800 ° of C.
Above-mentioned CaO/Zn-Al-O catalyzed by solid base biodiesel synthesis is as follows:
Take 3g CaO/Zn-Al-O solid base, put into the 250mL there-necked flask, add 38mL methyl alcohol, add hot reflux 30min, then add the 100mL rapeseed oil that is preheating to 65 ℃, the adjusting stir speed (S.S.) is 400r/min, reacts 4h under 65 ℃.Reactant liquor is cooled to room temperature, pours centrifuge tube into, the setting centrifuge speed is 6000r/min, and the time is 6min, and catalyst is removed in centrifugation.
Reactant liquor after the removal catalyst is poured in there-necked flask, and methyl alcohol is removed in air-distillation, and liquidus temperature is controlled at 140 ℃.After methyl alcohol has steamed, raffinate is cooled to room temperature, pour centrifuge tube into, the setting centrifuge speed is that 10000r/min, time are 6min, centrifugation again.The reactant liquor of centrifugal layering is poured in separatory funnel, namely obtained the biodiesel product after emitting lower floor's glycerine, the rapeseed oil conversion ratio is 94.6%.
Claims (4)
1. a biodiesel catalyst CaO/M-Al-O, is characterized in that: comprise active component CaO and composite oxides M-Al-O, the mass ratio of described active component CaO and catalyst CaO/M-Al-O
m(CaO)/
m(CaO/M-Al-O)=0.06～0.12; Wherein, M=Mg or Zn.
2. biodiesel catalyst CaO/M-Al-O according to claim 1 is characterized in that: described active component CaO high degree of dispersion in specific area at 150m
2/ g～250m
2/ g, pore volume are at 0.5 cm
3/ g～1.0cm
3/ g, average pore radius are in 5nm～12nm, mol ratio
n(M):
n(Al):
n(O) on the M-Al-O composite oxide carrier of=3:1:4.5.
3. the preparation method of biodiesel catalyst CaO/M-Al-O according to claim 1 and 2, is characterized in that: comprise the steps:
(1), with reference to natural magnesium aluminum hydrotalcite molecular formula: Mg
6Al
2(OH)
16CO
34H
2Element proportioning in O, in molar ratio
n(M):
n(Al):
n(OH
-):
n(CO
3 2-)=6:2:16:1～5, get 6 parts of M (NO
3)
26H
2O and 2 parts of Al (NO
3)
39H
2O, be made into water solution A; Get 16 parts of NaOH and 1 part～5 parts Na
2CO
3, be made into aqueous solution B;
(2), adopt and addition, water solution A and aqueous solution B are mixed and make it that coprecipitation reaction occur, through ageing, filtration, washing, drying, obtain the M-Al hydrotalcite;
(3), adopt the excess solution infusion process, with mass fraction, be 0.15～0.25 Ca (Ac)
2Aqueous solution dipping M-Al hydrotalcite, flood 10h～15h under 20 ℃～25 ℃, then filter, be drying to obtain Ca (Ac)
2/ M-Al hydrotalcite;
(4), at the temperature of 700 ℃～900 ℃, by Ca (Ac)
2/ M-Al hydrotalcite roasting 1h～5h, obtain biodiesel catalyst CaO/M-Al-O.
4. the preparation method of biodiesel catalyst CaO/M-Al-O according to claim 3, it is characterized in that: in step (2), water solution A and aqueous solution B mixed method are as follows: water solution A and aqueous solution B are respectively charged in two constant pressure funnels, in four-hole boiling flask, first put into deionized water, turn on agitator, regulate two constant pressure funnels, water solution A and aqueous solution B are added drop-wise in four-hole boiling flask and form mixed solution, regulating at any time a speed makes the pH value stabilization of mixed solution between 9～10, it is 1.00 mL/min～1.50 mL/min that the control water solution A splashes into speed, when M=Mg, controlling reaction temperature is 38 ℃～42 ℃, when M=Zn, controlling reaction temperature is 58 ℃～62 ℃.
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| CN105642268A (en) * | 2016-02-24 | 2016-06-08 | 太原工业学院 | Biodiesel catalyst X-Ca-Mg-Al-O and preparation method |
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| CN109759046A (en) * | 2019-01-25 | 2019-05-17 | 中国科学院过程工程研究所 | A kind of load type solid body base catalyst, preparation method and the method that furfurylidene-acetone and two furfurylidene-acetones are prepared by furfural and acetone |
| CN111468149A (en) * | 2020-05-15 | 2020-07-31 | 淮阴工学院 | Novel biodiesel solid catalyst KF/Ca-Mg-Al-O and preparation method and application thereof |
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| CN106536494A (en) * | 2014-08-06 | 2017-03-22 | 科学与工业研究委员会 | Preparation of functionalized castor oil derivatives by using solid acid and base catalysts |
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| CN109759046A (en) * | 2019-01-25 | 2019-05-17 | 中国科学院过程工程研究所 | A kind of load type solid body base catalyst, preparation method and the method that furfurylidene-acetone and two furfurylidene-acetones are prepared by furfural and acetone |
| CN111468149A (en) * | 2020-05-15 | 2020-07-31 | 淮阴工学院 | Novel biodiesel solid catalyst KF/Ca-Mg-Al-O and preparation method and application thereof |
| CN111468149B (en) * | 2020-05-15 | 2023-08-22 | 淮阴工学院 | Biodiesel solid catalyst KF/Ca-Mg-Al-O and preparation method and application thereof |
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