CN109876790A - A kind of CaO-MgO-Al2O3The method of catalyzed by solid base biodiesel synthesis - Google Patents
A kind of CaO-MgO-Al2O3The method of catalyzed by solid base biodiesel synthesis Download PDFInfo
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Abstract
The present invention discloses a kind of CaO-MgO-Al2O3The method of catalyzed by solid base biodiesel synthesis, the solid alkali preparation method is simple, low-temperature catalytic activity is high, easily separates with reaction system, at reaction time 4h, 75 DEG C of reaction temperature, catalyst amount 5%, alcohol oil rate 10:1, biodiesel product yield is up to 98.52%.
Description
Technical field
The invention belongs to chemical industry field of biological energy source, are related to a kind of CaO-MgO-Al2O3Mostly mesoporous netted catalyzed by solid base closes
At the method for biodiesel.
Background technique
Biodiesel is the mixture as vegetable fat and animal tallow through ester made of transesterification, most typically fatty
Sour methyl esters.Biodiesel is free of sulphur and aromatic hydrocarbons, Cetane number 52.9, density 0.85-0.89Kg/m substantially3, viscosity 3.5-
5.0Pas, boiling range<360 DEG C, flash-point>100 DEG C, sulfur content<0.02% are a kind of green safe renewable alternative energy sources.Work
Industry biodiesel synthesis is usually using homogeneous acid or base catalysis, such as sodium hydroxide, potassium hydroxide, sodium methoxide, sulfuric acid, hydrochloric acid, phosphorus
Acid etc..Although reaction can be made to be uniformly mixed using homogeneous catalysis preparation biodiesel, reaction rate is fast, high conversion rate, exists
The disadvantages of product separation is difficult, and catalyst cannot be reused, and consersion unit corrosivity is big, generates a large amount of acid-base waste fluids.It is non-equal
Phase solid acid or catalyzed by solid base can reduce side reaction saponification generation, catalyst be easily recycled it is reusable etc., therefore
The heterogeneous solid catalyst of exploitation high catalytic activity is paid high attention to.
Solid base, which refers to, can receive proton or provide electronics pair, have extremely strong supplied for electronic as catalytic active center or connect
By the ability of proton, free electron center is from surface O2-Or OH-Group.The forerunner of most alkaline earth oxide catalyst
Body does not have activity or activity is very low, only passes through high-temperature calcination, makes the basic sites of alkaline earth oxide that ability shape be exposed
Viability alkali center.Alkali and alkaline earth metal ions oxide belongs to a kind of strong base solid base catalyst, basic sites mainly from
In electronegative lattice oxonium ion O2-With the hydroxyl generated after surface adsorption water.Biodiesel research is prepared for ester exchange reaction
Mostly is CaO and MgO catalyst.Kouzu etc. obtains CaO catalyst by 900 DEG C of calcination of calcium carbonate, and as a result surface C aO has
Higher catalyzed transesterification activity, 1 hour fatty acid methyl ester mass yield is up to 93%.The more commercially available MgO such as Di Serio,
Mg(NO)2、Mg(OH)2、Mg(CO3)4.Mg(OH)2Four kinds of presomas calcine the activity of resulting magnesium oxide catalyzed ester exchange reaction,
By Mg (CO3)4.Mg(OH)2Calcining gained MgO alkalinity highest and catalyzed transesterification activity highest, but Cao Catalyst ester is handed over
Change reaction Ca2+It is lost serious and by-product to increase, expansion of these solid base catalysts there is also long-chain grease molecules in its hole
Dissipate the problems such as resistance is reunited, solid catalyst is acidproof, water resistance.
In view of the above-mentioned problems, the present invention discloses a kind of CaO-MgO-Al2O3Solid base catalyst and its catalysis grease with it is rudimentary
The method of alcohol transesterification reaction biodiesel synthesis.CaO-MgO-Al is first first prepared using homogeneous co-precipitation2O3Solid
Alkali presoma, then obtain by high-temperature roasting a kind of CaO-MgO-Al of the short thin square block of white2O3Solid base has catalysis
It is active high, easily separated recycling, the advantages such as active component not easily runs off, catalyst amount is low, catalytic reaction activity size order according to
Secondary is CaO-MgO-Al2O3≥CaO>CaO-MgO>CaO-Al2O3, anti-CaO leachability size order is successively CaO-MgO-
Al2O3>CaO-MgO>CaO-Al2O3> CaO, works as CaO-MgO-Al2O3Solid base catalyst and oil quality ratio 0.05:1, alcohol oil
Molar ratio 10:1,75 DEG C of reaction temperature, reaction time 4h, biodiesel fuel quality yield is up to 98%.
Summary of the invention
The purpose of the present invention
It is good and oily in low reaction temperatures, catalyst amount, alcohol that this hair purpose is intended to provide a kind of efficiently easily separated stability
Than the lower short thin square block CaO-MgO-Al for catalytically synthesizing biological diesel oil2O3Solid base and its catalytically synthesizing biological diesel oil
Method.
Technical solution of the present invention
1. a kind of CaO-MgO-Al2O3Solid base, it is characterised in that:
The CaO-MgO-Al2O3Solid base is the calcium that tri- kinds of metal body oxides of Ca, Mg, Al mutually adulterate formation
Based composite metal oxidate, wherein the molal weight ratio of Ca, Mg, Al are 1:0.125~0.375:0.125~0.375, basicity
PKa is 15.3~19.0；
The CaO-MgO-Al2O3Solid base is with Ca for main catalytic active component；
The CaO-MgO-Al2O3In solid base, MgO adulterates CaO and forms CaMgOXMetal composite oxide crystal phase rises
To solidification Ca2+, reduce the loss of CaO component effect；
The CaMgOXMetal composite oxide is Ca during MgO doping CaO2+、Mg2+It is total with exposed Lattice Oxygen
It is generated with combining, there is stronger alkalinity, wherein X=1~5；
The CaO-MgO-Al2O3In solid base, Al2O3It adulterates CaO and forms Ca12Al14O33Crystal phase, with CaO, CaMgOX
Crystal phase concerted catalysis, while also acting as solidification CaO, reducing CaO component loss effect；
The CaO-MgO-Al2O3In solid base, Al2O3Addition effect be the CaO-MgO- for generating short thin square block
Al2O3Solid base, while playing and increasing the specific surface area of active site and catalyst, solidifying CaO and reducing the shunting of CaO group
Mistake effect；
The CaO-MgO-Al2O3Solid base is cobblestone-appearance, length is 200~600nm, width be 100~
300nm；
The CaO-MgO-Al2O3There are the duct of ordered arrangement, cell wides inside solid base cobblestone-appearance particle
Between 1~3nm, this is conducive to the diffusion of reactant long-chain grease molecules and product in its duct；
The CaO-MgO-Al2O3There is wider distribution in solid base cobblestone-appearance intergranular space within the scope of 2~60nm,
This is conducive to the external diffusion of reactant long-chain grease molecules and product.
2. preparing the CaO-MgO-Al as described in 12O3The method of solid base, comprising the following steps:
(1) by CaCl2、Mg(CH3COO)2.4H2O、AlCl3.6H2O according to Ca, Mg, Al molar ratio be 1:0.125~
The metal precursor for being dissolved in and forming Ca, Mg, Al mixing in deionized water is mixed in the ratio of 0.375:0.125~0.375
Salting liquid, deionized water and Ca2+、Mg2+、Al3+The total ion molal weight ratio of three kinds of metals be 12~36:1,45~85 DEG C, in
Under 300~600 turns/min stirring, the mixed ammonium/alkali solutions containing sodium, potassium are slowly added into what Ca, Mg, Al above-mentioned were mixed
In metal precursor salting liquid, a kind of white suspension is formed, controls sodium, two metal ion species of potassium and Ca in white suspension2+、
Mg2+、Al3+The molal weight ratio of three metal ion species is 0.5~2:1, while the pH for controlling white suspension is 10~12, this
Sample is conducive to the formation being uniformly co-precipitated to inhibit to be co-precipitated speed；
The mixed ammonium/alkali solutions containing sodium, potassium are the mixture of sodium hydroxide or sodium carbonate and potassium hydroxide or potassium carbonate,
Wherein 2~5mol/L of 2~10mol/L of naoh concentration or concentration of sodium carbonate, 2~10 mol/L of concentration of potassium hydroxide or carbonic acid
The effect of 2~5mol/L of potassium concn, sodium hydroxide or potassium hydroxide is to make metal cation occur to be co-precipitated and adjust reaction solution
PH value maintain 10~12, finally make basic site exposure it is more, alkalinity enhancing, solid base specific surface area increase；
(2) after the completion of above (1) uniformly mixing coprecipitation process, be formed by white suspension in 55~75 DEG C,
100~200 turns/min stirs at low speed crystallization 20~for 24 hours, nucleus is formed by simultaneously not smashing in this way, so that Mg2+、Al3+It mixes
The lattice of miscellaneous CaO replaces more preferable progress, and crystallization makes crystal habit more complete at 55~75 DEG C, stands cooling, centrifugation point
From mixture, the mixed alkali liquor on upper layer is poured out, after adding deionized water washing lower layer's thick white body, is stirred evenly, again
White suspension is obtained, is centrifugated again, gained white is glued in such repetitive operation to white suspension pH=7.5~8.5
Thick body is in 100~120 DEG C of dry 8~12h, by the dry white solid grinding completed in powdered to get a kind of CaO-MgO-
Al2O3Solid base presoma；
(3) by the CaO-MgO-Al of above (2)2O3Solid base presoma is placed in box Muffle furnace, is starting with 100 DEG C
Temperature is warming up to 600~850 DEG C of 4~6h of roasting with 1~3 DEG C/min heating rate, so that tri- kinds of metals of Ca, Mg, Al are sloughed
Coupled hydroxyl generates the calcium based composite metal oxidate that corresponding three kinds of metal body oxides mutually adulterate and generates
Stronger alkalinity obtains a kind of CaO-MgO-Al of the short thin square block of thermodynamically stable white after cooling2O3Solid base.
3. by CaO-MgO-Al described in 12O3Solid base is used to be catalyzed grease and reacts preparation biodiesel with alcohols material
Method is as follows:
First by CaO-MgO-Al2O3Solid base grinding is in the powdered CaO-MgO-Al activated2O3Solid base, for urging
Change alcohols material and esterification and ester exchange reaction biodiesel synthesis crude product occur for grease, using separation and purification up to qualified
Biodiesel oil product；
The reaction condition of esterification with ester exchange reaction biodiesel synthesis occurs for the catalyzing alcohols substance and grease are as follows: alcohol
Substance and the molar ratio of grease are 10~20, CaO-MgO-Al2O3The mass ratio 0.02~0.07 of solid base and grease, reaction
65~95 DEG C of temperature, react 3~8h；
The alcohols material is at least one of methanol, ethyl alcohol, and the grease is soybean oil, palm oil, rapeseed oil, castor
At least one of sesame oil, waste cooking oil；
The separation and purification is that after reaction, cooling reaction mixture is centrifugated out in 6400~8000 turns/min
After solid base therein, then 30-50 mesh filters out a little solid base powder in reaction mixture, and remaining weak yellow liquid is
Saturated sodium chloride solution is added to life according still further to the volume ratio with biodiesel coarse product 0.1~0.2 by biodiesel coarse product
In object diesel oil crude product, it is thoroughly mixed and biodiesel coarse product demulsification is layered, recycle unreacted methanol, the white of lower layer
Muddy glycerol and saturated sodium chloride solution, the faint yellow biodiesel in the upper layer isolated continues to be washed with saturated sodium chloride solution
It washs, then vacuum rotary steam goes out after wherein a small amount of methanol, moisture and removing be sunken to a small amount of sodium chloride solution in bottom, gained clear
It is faint yellow oil mutually be purification biodiesel oil product, product quality yield be greater than 95%；
Recycle isolated CaO-MgO-Al2O3Solid base with methanol wash 3 times, 60~80 DEG C of vacuum drying 12h, sealing it is standby
It reuses.
Technical advantage and effect of the invention
It 1, is that catalytic active center plays major catalytic, Mg by foundation stone of Ca2+Being doped in CaO lattice has solidification
CaO, Ca is reduced2+Loss effect, and with exposed lattice oxonium ion O2-CaO/MgO complex oxide surface mixed crystal is formed, is had
Conducive to increase catalyst solid surface alkalinty active sites.
2, how mesoporous Al doping CaO advantageously form, and is formed by new crystal phase Ca12Al14O33Be conducive to solidify CaO and production
Raw more strong basicity positions.
3, prepared CaO-MgO-Al2O3Solid base is in short thin square block, is conducive to reactant grease molecules on its surface
Diffusion contact makes solid base surface alkalinty site be fully used in ester exchange reaction, keeps reaction more abundant.
4, prepared short thin square block CaO-MgO-Al2O3Catalyzed by solid base activity is high, reaction temperature is low, the reaction time
It is short, the catalyst amount of having is few, when alcohol oil rate is 10:1, reaction temperature is 75 DEG C, reaction time 4h, catalyst and oil quality ratio
0.05:1, biodiesel fuel quality yield is up to 98%.
Detailed description of the invention
Fig. 1 is the low-angle XRD spectra of catalyst sample: (a) CaO, (b) CaO-MgO (Ca, Mg molar ratio 4:1),
(c)CaO-Al2O3(Ca, Al molar ratio 4:1), (d) CaO-MgO-Al2O3(Ca, Mg, Al molar ratio 4:0.5:1.5), (e)
CaO-MgO-Al2O3(Ca, Mg, Al molar ratio 4:1:1), (f) CaO-MgO-Al2O3(Ca, Mg, Al molar ratio 4:1.5:0.5)
Low-angle XRD spectra.As shown in Figure 1, with the variation of catalyst solid constituent, tri- kinds of calcium based solid alkali catalyst of d, e, f
Principal crystalline phase there is no variation, be CaO (CaO, JCPD 82-1691,2 θ=32.30 °, 37.47 °, 54.03 °,
64.36 °, 67.60 °), but their CaO crystallographic plane diffraction peak intensity is changed: support type calcium based solid alkali (b), (c),
(d), the CaO crystallographic plane diffraction peak intensity of (e), (f) are all to weaken compared to pure CaO crystallographic plane diffraction peak intensity.This show MgO,
Al2O3It has loaded on CaO, the cube structure of CaO is caused to be distorted, so that crystallinity be made to reduce, diffraction maximum is to low angle
Migration correspondingly increases its interplanar distance d.This also illustrates MgO, Al2O3Load have a certain impact to interplanar distance,
The reason is that MgO, Al2O3Addition destroy Ca-O-Ca skeleton so that the degree of order of crystal reduces.In addition, passing through JCPD standard
Card compare analysis known to: in CaO-MgO other than CaO principal crystalline phase, there are also MgO crystal phase (the JCPD 77-2364:2 θ of MgO=
42.94 ° and 62.35 °)；CaO-MgO-Al2O3In other than CaO principal crystalline phase, have MgO and Al2O3Crystal phase (Al2O3JCPD 83-
θ=38.12 ° 2081:2,46.62 ° and 58.21 °), while at 29.3 °, 33.3 °, 34.9 °, 38.2 °, 46.5 °, 54.9 °,
56.1 °, there is mayenite Ca at 57.2 °, and 71.8 °12Al14O33(Mayenite) diffraction maximum of new crystal phase, furthermore exists
32.30 ° there is MgAlOXNew crystal phase, but overlapped by the covering of CaO crystal phase, but as this peak of the increase of Mg content becomes strong,
More confirm new crystal phase MgAlOXGeneration, new crystal phase plays catalytic action with CaO in Exchange Ester Process jointly.
Fig. 2 is the FT-IR spectrogram of catalyst sample: (a) CaO-Al2O3(Ca, Mg molar ratio 4:1), (b) CaO-MgO
(Ca, Mg molar ratio 4:1), (c) CaO-MgO-Al2O3(Ca, Mg, Al molar ratio 4:0.5:1.5), (d) CaO-MgO-Al2O3
(Ca, Mg, Al molar ratio 4:1:1), (e) CaO-MgO-Al2O3(Ca, Mg, Al molar ratio 4:1.5:0.5).From Figure 2 it can be seen that
1630cm-1The absorption peak at place belongs to the bending vibration of-OH key, belongs to-OH the vibration of mesopore molecular sieve physics water suction；
1479cm-1The absorption peak nearby occurred is CaO adsorption CO2The CO obtained afterwards3 2-The asymmetric stretching vibration peak of O-C-O key；
874cm-1For CO3 2-V2Absorption peak caused by peak, that is, O-C-O key out-of-plane bending vibration；400~800cm-1It is lattice in range
Oxonium ion O2-Absorption peak；450cm-1And 560cm-1For Ca-O-Al lattice oxonium ion O2-Vibration absorption peak, while inhaling herein
Receipts peak size is (b) > (d) > (e) > (c) > (a), and this phenomenon occur is because Ca and Al binding ability are better than Mg, and Al is easier to
It is doped into and is doped in CaO lattice, generate mayenite Ca12Al14O33Play the role of solidifying CaO loss, therefore surface is inhaled in (a) CaO
Attached CO2Amount it is minimum, (b) in CaO adsorption CO2Amount it is maximum, and there is mayenite Ca in one XRD spectra of figure12Al14O33
(Mayenite) the diffraction maximum result of new crystal phase matches.
Fig. 3 is the CO of catalyst sample2- TPD figure: (a) CaO-MgO-Al2O3(Ca, Mg, Al molar ratio 4:0.5:
1.5)、(b)CaO-MgO-Al2O3(Ca, Mg, Al molar ratio 4:1:1), (c) CaO-MgO-Al2O3(Ca, Mg, Al molar ratio 4:
1.5:0.5), (d) CaO-MgO (Ca, Mg molar ratio 4:1), (e) CaO-Al2O3(Ca, Mg molar ratio 4:1), wherein the desorption of (a)
Temperature is 690 DEG C, and desorption temperature (b) is 730 DEG C, and desorption temperature (c) is 720 DEG C, and desorption temperature (d) is 723 DEG C,
(e) desorption temperature is 710 DEG C, base strength be successively from big to small in (b) > (d) > (c) > (e) > (a), total alkali content from greatly to
Small is successively (b) > (c) > (a) > (d) > (e).
Fig. 4 is the N of catalyst sample2Adsorption-desorption figure: (a) CaO-MgO-Al2O3(Ca, Mg, Al molar ratio 4:0.5:
1.5)、(b)CaO-MgO-Al2O3(Ca, Mg, Al molar ratio 4:1:1), (c) CaO-MgO-Al2O3(Ca, Mg, Al molar ratio 4:
1.5:0.5)、(d)CaO-Al2O3(Ca, Al molar ratio 4:1), (e) CaO-MgO (Ca, Mg molar ratio 4:1), sample (a), (b),
(c), (d) Adsorption and desorption isotherms belong to type III thermoisopleth, and hysteresis loop belongs to H3Type.As can be seen that adsorption isotherm is in low pressure
Area is gentle and adsorbance is smaller, illustrates that catalyst sample micropore is less, and as relative pressure increases, adsorbance rises on foot, and explanation is urged
Agent sample hole is mainly mesoporous and minimal amount macropore, this also with the CaO-MgO-Al in Fig. 52O3Catalyst series sample well
Diameter is distributed between 2-60nm, is mainly distributed between 3-4nm and is consistent.CaO-MgO-Al2O3Serial solid catalyst sample H3It is stagnant
Ring afterwards can be inferred that there is catalyst sample sheet-like particle loosely-packed to form slit pore, and sample (e) belongs to type III isothermal
Line is relative to P/PoIt is less in low-pressure area adsorbance in convex curve, become larger as opposite pressure increases adsorbance, no lag
Ring, but be mainly mesoporous and minimal amount macropore according to Fig. 5 pore-size distribution still derived sample (e) hole, pore-size distribution is in 2-60nm
Between, it is mainly distributed between 3-4nm.
Fig. 5 is catalyst sample particulate interspaces degree (aperture is labeled as in figure) distribution map: (a) CaO-MgO-Al2O3(Ca、
Mg, Al molar ratio 4:0.5:1.5)；(b)CaO-MgO-Al2O3(Ca, Mg, Al molar ratio 4:1:1)；(c)CaO-MgO-Al2O3
(Ca, Mg, Al molar ratio 4:1.5:0.5)； (d)CaO-Al2O3(Ca, Al molar ratio 4:1)；(e) CaO-MgO (Ca, Mg molar ratio
4:1).(a), there is wider distribution in gap within the scope of 2~60nm between (b), (c), (d), (e) five kinds of sample particles, wherein 2
~5nm distribution is slightly more, this is conducive to the external diffusion of reactant long-chain grease molecules and product.
Fig. 6 is the thermogravimetric analysis figure of catalyst sample.CaO-MgO-Al as seen from Figure 62O3(Ca, Mg, Al molar ratio 4:1:
1) thermal decomposition process of catalyst sample is divided into three phases: the Ith stage (50~240 DEG C) is metal oxide mesoporous molecular
The removing of physics water suction is sieved, the IIth stage (240~510 DEG C) is the removing of hydroxyl in metal hydroxides；IIIth stage (510
~760 DEG C) be metal oxide slowly start to be sintered, surface area starts to reduce, and eventually forms spinelle.
Fig. 7 is CaO-MgO-Al2O3The SEM of (Ca, Mg, Al molar ratio 4:1:1) schemes.From fig.7, it can be seen that CaO-MgO-Al2O3
(Ca, Mg, Al molar ratio 4:1:1) catalyst granules is in cobblestone-appearance, and length is 200~600nm, width is 100~300nm.
Fig. 8 is CaO-MgO-Al2O3(Ca, Mg, Al molar ratio 4:1:1) TEM figure.Sample can be obviously observed from Fig. 8
Intragranular portion there are the duct of ordered arrangement, cell wide between 1~3nm, this be conducive to reactant long-chain grease molecules with
Diffusion of the product in its duct.
Technical solutions and their implementation methods of the present invention are explained below by embodiment.
Embodiment 1
1.CaO-MgO-Al2O3The preparation of mostly mesoporous netted solid base
(1) by CaCl2、Mg(CH3COO)2.4H2O、AlCl3.6H2O is 1:0.25:0.25's according to Ca, Mg, Al molar ratio
Ratio mixing is dissolved in formation calcium and magnesium aluminium precursor salt solution, deionized water and Ca in deionized water2+、Mg2+、Al3+Three kinds
Total ion molar ratio of metal is 20, at 60 DEG C under 400 turns/min stirring, sodium hydroxide is slowly added into aforementioned
Calcium and magnesium aluminium precursor salt solution in, wherein naoh concentration be 6mol/L, sodium hydroxide and Ca2+、Mg2+、Al3+Three kinds of gold
The total ion molar ratio belonged to is 1.5:1, while controlling the speed and amount that lye is added, and is conducive to inhibiting co-precipitation speed
Even co-precipitation is formed, while the pH for the white suspension that three kinds of metal hydroxides of itself and calcium and magnesium aluminium are mixed to form is
11。
(2) white suspension is formed after the completion of above (1) is uniformly mixed generation coprecipitation process, then at 65 DEG C, 150
Turn/min stirs at low speed crystallization 22h, and it is not smashing molding crystal form in this way while same order elements is more preferably carried out, the crystalline substance at 65 DEG C
Change so that crystal habit is more complete, stand cooling, centrifugally separating mixture pours out upper layer mixed alkali liquor, be added again go from
Sub- water washing lower layer thick white body, is stirred evenly with glass bar, regains white suspension, be centrifugated again, in this way
Repetitive operation is to white suspension pH=8, by gained thick white body in 110 DEG C of dry 10h, by the dry white solid completed
Grinding is in powdered to get a kind of CaO-MgO-Al2O3Solid base presoma.
(2) by CaO-MgO-Al2O3Mostly mesoporous netted solid base presoma is placed in box Muffle furnace with 100 DEG C as starting
Temperature is warming up to 700 DEG C of roasting 5h with 2 DEG C/min heating rate, wherein being initial temperature with 100 DEG C, being to terminate temperature with 700 DEG C
Degree preferably simulates the temperature-rise period of TG test, preferably probes into CaO-MgO-Al2O3Mostly mesoporous netted solid base internal structure
Internal structure and various substances thermal decomposition temperature, pass through TG-DTA tracing analysis CaO-MgO-Al2O3It is mostly mesoporous netted solid
The thermodynamic stability of body alkali thermal decomposition, makes tri- kinds of metals of Ca, Mg, Al slough coupled hydroxyl in 700 DEG C of high-temperature roastings
Base generates corresponding metal composite oxide and generates stronger alkalinity, and gained white solid is a kind of stable after cooling
CaO-MgO-Al2O3Solid base catalyst.
2.CaO-MgO-Al2O3Catalyzed by solid base biodiesel synthesis
By CaO-MgO-Al obtained by 2.5g2O3Solid base, 50g soybean oil, 25g methanol are added in reactor, catalyst
Dosage is the 5% of oil quality, and reaction temperature is 75 DEG C, and reaction time 4h is cooled to room temperature after reaction, passes through centrifugation
Catalyst sedimentation to bottom, biodiesel coarse product centrifugation to upper layer, first split-phase are isolated the yellowish colour biological bavin in upper layer by separation
Oily crude product, after filtering out catalyst, filter cake is washed 3 times with methanol, after 60 DEG C are dried in vacuo 12 hours, as catalyst under
Secondary reuse, reaction product first passes through revolving and removes recycling methanol, then is washed repeatedly with saturated brine and remove residual methanol, obtains
Biodiesel product quality yield 98.52%, prepared biodiesel oil product index Cetane number 52, density 0.86Kg/m3、
Viscosity 4.3Pas, 110 DEG C of flash-point, sulfur content 0.015%.
2 operating procedure of embodiment is with case study on implementation 1, but CaO-MgO-Al2O3The molar ratio of Ca, Mg, Al are in solid base
4:0.5:1.5 obtains biodiesel product quality yield 95.13%.
3 operating procedure of embodiment is with case study on implementation 1, but CaO-MgO-Al2O3Ca, Mg, Al in mostly mesoporous netted solid base
Molar ratio be 4:1.5:0.5, obtain biodiesel product quality yield 95.65%.
4 operating procedure of embodiment is with case study on implementation 1, but CaO-MgO-Al2O3The molar ratio of Ca, Mg, Al are in solid base
4:1:0 obtains biodiesel product quality yield 95.00%.
5 operating procedure of embodiment is with embodiment 1, but CaO-MgO-Al2O3The quality molar ratio of Ca, Mg, Al in solid base
For 4:0:1, biodiesel product quality yield 95.13% is obtained.
6 operating procedure of embodiment is with case study on implementation 1, but CaO-MgO-Al2O3Ca, Mg, Al in mostly mesoporous netted solid base
Quality molar ratio is 4:0:1.5, obtains biodiesel product quality yield 95.03%.
7 operating procedure of embodiment is with case study on implementation 1, but CaO-MgO-Al2O3Ca, Mg, Al in mostly mesoporous netted solid base
Quality molar ratio be 4:1.5:0, obtain biodiesel product quality yield 96.03%.
8 operating procedure of embodiment is with embodiment 1, but maturing temperature is 550 DEG C, obtains biodiesel reaction product quality yield
95.66%.
9 operating procedure of embodiment is with embodiment 1, but maturing temperature is 600 DEG C, obtains biodiesel product quality yield
95.72%.
10 operating procedure of embodiment is with embodiment 1, but maturing temperature is 650 DEG C, obtains biodiesel product quality yield
98.52%.
11 operating procedure of embodiment is with embodiment 1, but maturing temperature is 750 DEG C, obtains biodiesel product quality yield
96.40%.
12 operating procedure of embodiment is with embodiment 1, but the reaction time is 2h, obtains biodiesel product quality yield
95.32%.
13 operating procedure of embodiment is with embodiment 1, but the reaction time is 6h, obtains biodiesel product quality yield
96.43%.
14 operating procedure of embodiment is with embodiment 1, but the reaction time is 8h, obtains biodiesel product quality yield
97.40%.
15 operating procedure of embodiment is with embodiment 1, but the reaction time is 10h, obtains biodiesel product quality yield
96.65%.
16 operating procedure of embodiment is with embodiment 1, but reaction temperature is 60 DEG C, obtains biodiesel product quality yield
95.30%.
17 operating procedure of embodiment is with embodiment 1, but reaction temperature is 80 DEG C, obtains biodiesel product quality yield
98.52%.
18 operating procedure of embodiment is with embodiment 1, but reaction temperature is 90 DEG C, obtains biodiesel product quality yield
98.27%.
19 operating procedure of embodiment is with embodiment 1, but reaction temperature is 100 DEG C, obtains biodiesel product quality yield
97.36%.
20 operating procedure of embodiment is with embodiment 1, but quantity of methyl alcohol is 16g, obtains biodiesel product quality yield
95.00%.
21 operating procedure of embodiment is with embodiment 1, but quantity of methyl alcohol is 34g, obtains biodiesel product quality yield
95.85%.
22 operating procedure of embodiment is with embodiment 1, but quantity of methyl alcohol is 46g, obtains biodiesel product quality yield
97.20%.
23 operating procedure of embodiment is with embodiment 1, but quantity of methyl alcohol is 58g, obtains biodiesel reaction product quality yield
97.15%.
24 operating procedure of embodiment is with embodiment 1, but catalyst is the 2nd recycling, obtains biodiesel product quality
Yield 97.77%.
25 operating procedure of embodiment is with embodiment 1, but catalyst is the 3rd recycling, obtains biodiesel reaction product
Mass yield 96.91%.
26 operating procedure of embodiment is with embodiment 1, but catalyst is the 4th recycling, obtains biodiesel product quality
Yield 95.65%.
27 operating procedure of embodiment is with embodiment 1, but catalyst is the 5th recycling, obtains biodiesel product quality
Yield 95.13%.
2 Examples 1 to 2 of table, 6 operating condition and reaction result
Claims (3)
1. a kind of CaO-MgO-Al2O3Solid base, it is characterised in that:
The CaO-MgO-Al2O3Solid base is multiple for the calcium base that tri- kinds of metal body oxides of Ca, Mg, Al mutually adulterate formation
Metal oxide is closed, wherein the molal weight ratio of Ca, Mg, Al are 1:0.125 ~ 0.375:0.125 ~ 0.375, and basicity pKa is
15.3~19.0；
The CaO-MgO-Al2O3Solid base is with Ca for main catalytic active component；
The CaO-MgO-Al2O3In solid base, MgO adulterates CaO and forms CaMgOXMetal composite oxide crystal phase plays solid
Change Ca2+, reduce the loss of CaO component effect；
The CaMgOXMetal composite oxide is Ca during MgO doping CaO2+、Mg2+It is tied jointly with exposed Lattice Oxygen
Symphysis is at having stronger alkalinity, wherein X=1 ~ 5；
The CaO-MgO-Al2O3In solid base, Al2O3It adulterates CaO and forms Ca12Al14O33Crystal phase, with CaO, CaMgOXCrystal phase
Concerted catalysis, while also acting as solidification CaO, reducing CaO component loss effect；
The CaO-MgO-Al2O3In solid base, Al2O3Addition effect be the CaO-MgO-Al for generating short thin square block2O3
Solid base, while playing and increasing the specific surface area of active site and catalyst, solidifying CaO and reducing CaO component and be lost and making
With；
The CaO-MgO-Al2O3Solid base is cobblestone-appearance, and length is 200 ~ 600nm, width is 100 ~ 300nm；
The CaO-MgO-Al2O3There are the duct of ordered arrangement inside solid base cobblestone-appearance particle, cell wide 1 ~
Between 3nm, this is conducive to the diffusion of reactant long-chain grease molecules and product in its duct；
The CaO-MgO-Al2O3There is wider distribution in solid base cobblestone-appearance intergranular space within the scope of 2 ~ 60nm, this is advantageous
In the external diffusion of reactant long-chain grease molecules and product.
2. preparing CaO-MgO-Al as described in claim 12O3The method of solid base, feature the following steps are included:
(1) by CaCl2、Mg(CH3COO)2 .4H2O、AlCl3 .6H2O is 1:0.125 ~ 0.375 according to Ca, Mg, Al molar ratio:
The metal precursor salting liquid for being dissolved in and forming Ca, Mg, Al mixing in deionized water is mixed in 0.125 ~ 0.375 ratio,
Deionized water and Ca2+、Mg2+、Al3+The total ion molal weight ratio of three kinds of metals is 12 ~ 36:1, at 45 ~ 75 DEG C, in 300 ~ 600
Turn/min stirring under, it is molten that the aqueous slkali of sodium or potassium is slowly added into the metal precursor salt that Ca, Mg, Al above-mentioned are mixed
In liquid, a kind of white suspension is formed, controls sodium, two metal ion species of potassium and Ca in white suspension2+、Mg2+、Al3+Three kinds of gold
The molar ratio for belonging to ion is 0.5 ~ 2:1, while the pH for controlling white suspension is 10 ~ 12, in this way to inhibit co-precipitation speed to have
Conducive to the formation being uniformly co-precipitated；
The sodium, potassium aqueous slkali be 2 ~ 10 mol/L of sodium hydroxide or potassium hydroxide, sodium hydroxide or concentration of potassium hydroxide, hydrogen
The effect of sodium oxide molybdena or potassium hydroxide is that the pH value for making metal cation occur to be co-precipitated and adjust reaction solution maintains 10 ~ 12,
Increase more basic site exposure, alkalinity enhancing, solid base specific surface area；
(2) after the completion of above (1) uniformly mixing coprecipitation process, white suspension is formed by 55 ~ 75 DEG C, 100 ~ 200
Turn/min stirs at low speed crystallization 20 ~ for 24 hours, nucleus is formed by simultaneously not smashing in this way, so that Mg2+、Al3+Adulterate the crystalline substance of CaO
Lattice replace more preferable progress, and crystallization makes crystal habit more complete at 55 ~ 75 DEG C, stand and cool down, centrifugally separating mixture,
The mixed alkali liquor on upper layer out stirs evenly after adding deionized water washing lower layer's thick white body, regains white suspension
Liquid is centrifugated again, such repetitive operation to white suspension pH=7.5 ~ 8.5, by gained thick white body 100 ~ 120
DEG C dry 8 ~ 12h, by the dry white solid grinding completed in powdered to get a kind of CaO-MgO-Al2O3Solid base forerunner
Body；
(3) by the CaO-MgO-Al of above (2)2O3Solid base presoma is placed in box Muffle furnace, be initial temperature with 100 DEG C,
Be warming up to 600 ~ 850 DEG C of 4 ~ 6h of roasting with 1 ~ 3 DEG C/min heating rate so that tri- kinds of metals of Ca, Mg, Al slough it is coupled
Hydroxyl generates the calcium based composite metal oxidate that corresponding three kinds of metal body oxides mutually adulterate and generates stronger alkalinity,
A kind of CaO-MgO-Al of the short thin square block of thermodynamically stable white is obtained after cooling2O3Solid base.
3. by CaO-MgO-Al described in claim 12O3Solid base reacts the biological bavin of preparation with alcohols material for being catalyzed grease
The method of oil, it is characterised in that:
First by CaO-MgO-Al2O3Solid base grinding is in the powdered CaO-MgO-Al activated2O3Solid base is used for catalyzing alcohols
Esterification and ester exchange reaction biodiesel synthesis crude product occur for substance and grease, using separation and purification up to qualified biology
Diesel product；
The reaction condition of esterification with ester exchange reaction biodiesel synthesis occurs for the catalyzing alcohols substance and grease are as follows: alcohols object
Matter and the molar ratio of grease are 10 ~ 20, CaO-MgO-Al2O3The mass ratio 0.02 ~ 0.07 of solid base and grease, reaction temperature 65 ~
95 DEG C, react 3 ~ 8h；
The alcohols material is at least one of methanol, ethyl alcohol, and the grease is soybean oil, palm oil, rapeseed oil, castor-oil plant
At least one of oil, waste cooking oil；
The separation and purification is that after reaction, cooling reaction mixture is centrifugated out therein in 6400 ~ 8000 turns/min
After solid base, then 30-50 mesh filters out a little solid base powder in reaction mixture, and remaining weak yellow liquid is biological bavin
Saturated sodium chloride solution is added to biodiesel according still further to the volume ratio with biodiesel coarse product 0.1 ~ 0.2 by oily crude product
In crude product, it is thoroughly mixed the unreacted methanol, white opacity that lower layer is recycled to biodiesel coarse product demulsification layering
Glycerol and saturated sodium chloride solution, the faint yellow biodiesel in the upper layer isolated continues to be washed with saturated sodium chloride solution, then subtracts
Pressure rotates out after wherein a small amount of methanol, moisture and removing be sunken to a small amount of sodium chloride solution in bottom, gained clear it is yellowish
Color oil is mutually the biodiesel oil product of purification, and product quality yield is greater than 95%；
Recycle isolated CaO-MgO-Al2O3Solid base washs 3 times with methanol, 60 ~ 80 DEG C of vacuum drying 12h, sealing is standby repeats to make
With.
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