CN102744053B - Composite solid base CaO-Al2O3 and method for preparing biodiesel oil by catalysis of waste vegetable oil with the same - Google Patents

Composite solid base CaO-Al2O3 and method for preparing biodiesel oil by catalysis of waste vegetable oil with the same Download PDF

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CN102744053B
CN102744053B CN201110403553.8A CN201110403553A CN102744053B CN 102744053 B CN102744053 B CN 102744053B CN 201110403553 A CN201110403553 A CN 201110403553A CN 102744053 B CN102744053 B CN 102744053B
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cao
catalyst
biodiesel
mass ratio
oil
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CN102744053A (en
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张前前
禹变变
梁生康
李苓
陆金仁
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Ocean University of China
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Abstract

The present invention provides a composite solid base CaO-Al2O3 and a method for preparing a biodiesel oil, wherein a mass ratio of CaO to Al2O3 in a catalyst is 4.5:1, and the catalyst has an excellent catalytic activity. The method for preparing a biodiesel oil by catalysis with the CaO-Al2O3 comprises: carrying out a reaction under a certain conditions, wherein a molar ratio of an alcohol to oil is 6:1-12:1, a cosolvent is n-hexane having a weight percentage of 5-80 wt% or a biodiesel oil having a weight percentage of 5-20 wt%, a heating temperature is 60-65 DEG C, an amount of the catalyst is 1-5 wt%; carrying out centrifugate to separate a solid catalyst; and carrying out standing and layering, wherein the upper layer is the biodiesel oil. The preparation method for the biodiesel oil in the present invention has the following advantages that: the yield is more than 98%; the reaction time is shortened to 40-60 minutes; the efficiency is close to the efficiency of a homogeneous catalyst; the catalyst can be reused more than 70 times, and the biodiesel oil yield is more than 98%; and the cost is reduced, and the method has characteristics of rapidness and simple operation, and provides great significances for new energy industry development and environmental protection.

Description

Complex solid alkali CaO-Al 2o 3and catalysis waste vegetable oil is prepared the method for biodiesel
Technical field
The invention belongs to oil chemistry and Application in Chemical Engineering field, relate to diesel preparation field, relate in particular to a kind of complex solid alkali CaO-Al 2o 3and catalysis waste vegetable oil is prepared the method for biodiesel.
Background technology
In recent years, the air pollution increasingly exhausted and that oil combustion causes of world petroleum resource impels people to find new alternative energy source.Biodiesel is that discarded object taking vegetable fat, animal fat, their processing or after using and microbial grease are as raw material, carry out with low-carbon alcohols the LCFA mono alkyl ester that ester exchange reaction obtains, the feature of environmental protection that it is outstanding and recyclability cause the great attention of countries in the world.The U.S., European Union and Japan have taken the lead in producing and use biodiesel.
Biodiesel not yet replaces petrochemical industry oil at present, and reason is that its cost is far above petrochemical industry oil.According to statistics, the cost of material of biodiesel accounts for 70%～85% of total production cost, and therefore, finding cheap raw material becomes the matter of utmost importance that reduces biodiesel cost.The fundamental realities of the country of having a large population and a few land has determined China's development biodiesel, can not walk the way of " strive ground, strive grain with people with agriculture ", waste vegetable oil reclaims price lower (being about 3800 yuan/ton) because of it, for 1/2nd of general vegetable oil price, become one of biodiesel raw material main source.
The preparation method of biodiesel has direct mixing method, micro emulsion method, high temperature pyrolytic cracking and ester-interchange method, and wherein ester-interchange method is the method the most generally adopting in biodiesel preparation.According to catalyst difference, be divided into supercritical fluid technique method, enzyme catalysis method, acid-catalyzed transesterification method and base-catalyzed transesterification method.Under super critical condition, methyl alcohol has hydrophobicity and compared with low-k, at this moment grease can be dissolved in the formation of methanol single_phase system completely, and without catalyst, post processing is easy, and the reaction time is 1h; But due to the reaction condition of high temperature, high pressure, high to equipment requirement, energy consumption is larger.Enzymatic transesterification has a lot of advantages, and the reaction time is 1h left and right, but lipase is expensive, and easy inactivation, has hindered its suitability for industrialized production for biodiesel.Adopt homogeneous acid catalysis or base catalysis method, reaction time is generally 30min～60min, but all exist catalyst be not easy with product separation, product in the acidand basecatalysts that exists must neutralize washing, thereby produce a large amount of sewage, and acid base catalysator can not be reused, bring the higher problem such as catalyst cost and acid base catalysator etching apparatus.
In order to solve the separation problem of catalyst and product, solid base heterogeneous catalytic reaction becomes important research direction.Solid alkali catalytic method has the significant advantages such as equipment is simple, post processing is easy, non-environmental-pollution, in prior art, the reaction time of most solid base heterogeneous catalytic reaction biodiesel processed exceedes 1h, can make the reaction time shorten within 1h only for a few system such as SrO, SrO/MgO, but the research of catalyst-free regenerability.Therefore, efficient and renewable solid base catalyst remains urgent problem.
Summary of the invention
For utilizing at present solid base heterogeneous catalysis to prepare the defect that biodiesel cost is high, the catalytic reaction time long and catalyst can not reuse, the object of the present invention is to provide a kind of complex solid alkali CaO-Al 2o 3and catalysis waste vegetable oil is prepared the method for biodiesel, the present invention not only provides novel complex solid base catalyst that can Efficient Conversion waste vegetable oil, and, on definite Structure and form of this catalyst and the basis of waste vegetable oil purification condition, the process conditions of preparing biodiesel taking waste vegetable oil as raw material are optimized, determine that impact transforms the key factor of waste vegetable oil, thereby set up method quick, low cost is prepared biodiesel with waste vegetable oil.
For achieving the above object, the present invention adopts following technical proposals to be achieved:
The invention provides a kind of complex solid alkali CaO-Al 2o 3catalyst, CaO and Al in described catalyst 2o 3mass ratio be optimized for 4.5: 1, described catalyst is porous network structure, specific area is 15.971m 2g -1, porosity 0.4311, pore volume 0.045cm 3g -1, aperture 11.28nm, CaO and Al 2o 3bonding generates new crystalline phase Ca 12al 14o 33.
Described new crystalline phase Ca 12al 14o 33diffraction maximum be 20.9 °, 23.3 °, 27.7 °, 29.3 °, 33.3 °, 34.9 °, 36.5 °, 38.2 °, 41.1 °, 46.5 °, 54.9 °, 56.1 °, 57.2 °, 60.5 ° and 71.8 °.
The present invention also provides described complex solid alkali CaO-Al 2o 3the preparation method of catalyst, one of described preparation method is polishing, to CaCl 2in solution, add Pidolidone, CaCl 2with the mass ratio of Pidolidone be 200: 1～300: 1, stir make it dissolve after, it is slowly joined and CaCl 2the Na of equimolar amounts 2cO 3in solution, suction filtration after 20～80 DEG C of reaction 1～6h, respectively with distilled water and ethanol washing 2～3 times, 100 DEG C of above dry 1～5h, get final product to obtain the CaCO of tool Mesoporous Spheres structure 3, by CaCO 3more than 400 DEG C, calcine 1～4h, must there is the CaO of Mesoporous Spheres structure;
By the above-mentioned CaCO making 3with Al (OH) 3be to mix at 100: 19 in mass ratio, be placed in mortar and grind 10～120min, after fully mixing, in more than 400 DEG C calcining 1～5h, the drier that is placed in to be cooled, obtains CaO and Al 2o 3mass ratio is the soild alkali catalyst CaO-Al of 4.5: 1 2o 3.
The present invention also provides described complex solid alkali CaO-Al 2o 3the preparation method of catalyst, described preparation method's two is coprecipitation, by Al (NO 3) 39H 2o and CaCl 2be to mix and dissolve and to obtain calcium aluminium mixed liquor at 0.82: 1 in mass ratio, take mass ratio and be the Na of 7.24: 1 2cO 3and NaOH, add distilled water to make it to dissolve completely, slowly splash in described calcium aluminium mixed liquor with separatory funnel, stir, ageing 1～12h at 20～100 DEG C, suction filtration, washing, more than 400 DEG C calcines 1～5h drier that is placed in to be cooled, obtains CaO and Al 2o 3mass ratio is the soild alkali catalyst CaO-Al of 4.5: 1 2o 3.
The present invention also provides with complex solid alkali CaO-Al 2o 3catalysis waste vegetable oil is prepared the method for biodiesel, the discarded plant molar equivalent of low-carbon alcohols and purifying 6: 1～12: 1, and 5～80wt% of the waste vegetable oil that cosolvent is purifying, 60～65 DEG C of heating-up temperatures, complex solid base catalyst CaO-Al 2o 31～5wt% of the consumption waste vegetable oil that is purifying, the reaction time is 40～60min, centrifugation solid catalyst, rotary evaporation reclaims solvent, stratification separates lower floor's glycerine, upper strata is biodiesel.
Further improvement to technique scheme: it is characterized in that described low-carbon alcohols is methyl alcohol.
Further improvement to technique scheme: the n-hexane that described cosolvent is 5～80wt% or the biodiesel of 5～20wt%.
Further improvement to technique scheme: described catalyst CaO-Al 2o 3reuse more than 70 times, productive rate reaches more than 98%.
Compared with prior art, advantage of the present invention and good effect are:
1, efficient.The present invention adopts polishing and coprecipitation to synthesize the calcium based solid alkali catalyst CaO-Al of high efficiency, low cost 2o 3, wherein especially with CaO-Al 2o 3(4.5: 1) show fabulous catalytic activity.With CaO-Al 2o 3catalysis waste vegetable oil is prepared the method for biodiesel, is ensureing that yield is greater than under 98% prerequisite, and the reaction time of preparation biodiesel shortens to 40～60min, and uses the equal efficiency of homogeneous catalyst.
2, reusable.Catalyst of the present invention is processed without regeneration, reusable more than 70 times.
3, stable.The compound base catalyst of synthesized of the present invention has the advantages that catalytic activity is high, Reusability performance is good, and catalyst is in reusable situation, and biodiesel production rate is all more than 98%.
4, cost is low.The present invention uses waste vegetable oil for raw material, and cost reduces greatly, and fast, simple to operate, for promoting New Energy Industry, protection of the environment, significant.
Read by reference to the accompanying drawings after the specific embodiment of the present invention, it is clearer that the other features and advantages of the invention will become.
Brief description of the drawings
Fig. 1 is preparation method's flow chart of biodiesel of the present invention.
Fig. 2 is SEM figure (the A.CaO x 5.00k of different catalysts of the present invention; B.CaO-Al 2o 3(2: 1) x 5.00k; CaO-Al 2o 3(4.5: 1) x 5.00k; D.CaO-Al 2o 3(4.5: 1) x 30.00k).
Fig. 3 is XRD figure ((a) new system CaO of different catalysts of the present invention; (b) new system CaO-Al 2o 3; (c) CaO uses 1 not calcining; (d) CaO-Al 2o 3(4.5: 1) are used 1 not calcining; (e) CaO-Al 2o 3(4.5: 1) are used 2 not calcinings; (f) CaO-Al 2o 3(4.5: 1) are used 600 DEG C of calcining 2h 1 time; (g) CaO-Al 2o 3(4.5: 1) are used 600 DEG C of calcining 2h 20 times).
Fig. 4 is IR figure ((a) CaO-Al of different catalysts of the present invention 2o 3(2: 1), (b) CaO-Al 2o 3(3: 1), (c) CaO-Al 2o 3(4: 1), (d) CaO-Al 2o 3(4.5: 1), (e) CaO-Al 2o 3(5: 1)).
Fig. 5 is biodiesel production rate and catalyst CaO-Al in the present invention 2o 3(4.5: 1) reuse number of times graph of a relation.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, technical scheme of the present invention is described in further detail.
Embodiment 1
1, novel C aCO 3and the preparation of CaO
Measure 500mL 0.100～2.00molL -1caCl 2, add 0.500～3.000g Pidolidone, stir and make it to dissolve, slowly join 500mL 0.100～2.00molL -1na 2cO 3in, suction filtration after 20～80 DEG C of reaction 1～6h, respectively with distilled water and ethanol washing 2～3 times, 100 DEG C of above dry a few hours, gets final product to such an extent that have a CaCO of special Mesoporous Spheres structure 3.By CaCO 3more than 400 DEG C, calcine 1～4h, must there is the CaO of analog structure.
2, soild alkali catalyst CaO-Al 2o 3preparation
(1) polishing: by the Al of 1.529g (OH) 3respectively with the above-mentioned CaCO making 30.396g, 1.786g, 3.571g, 5.358g, 7.144g, 8.037g, 8.930g mix, and are placed in mortar and grind 10～120min, and after fully mixing, in more than 400 DEG C calcining 1～5h, the drier that is placed in to be cooled, obtains CaO and Al 2o 3mass ratio is respectively the CaO-Al of 1: 4.5,1: 1,2: 1,3: 1,4: 1,4.5: 1,5: 1 2o 3solid base catalyst.
(2) coprecipitation: by a certain proportion of CaCl 2and Al (NO 3) 39H 2o mixes and dissolves, and takes NaOH and the Na of respective quality 2cO 3, add distilled water to make it to dissolve completely, slowly splash in above-mentioned calcium aluminium mixed liquor with separatory funnel, stir ageing 1～12h at 20～100 DEG C, suction filtration, washing.More than 400 DEG C calcine 1～5h drier that is placed in to be cooled, obtain CaO and Al 2o 3mass ratio is respectively the CaO-Al of 1: 4.5,1: 1,4.5: 1 2o 3solid base catalyst.Reagent weighing data is in table 1.
Table 1: coprecipitation is prepared CaO-Al 2o 3the each reagent of solid base catalyst weighs table
3, CaO-Al 2o 3the sign of solid base catalyst
CaO-Al 2o 3the morphology analysis of solid base catalyst is shown in Fig. 2, Fig. 3 and Fig. 4.The form of observing different catalysts surface by ESEM (SEM), the results are shown in Figure 2.Fig. 2 A is that the above-mentioned CaO making amplifies the SEM figure that 5.00k obtains, and as can be seen from the figure CaO has special holey spherical structure, and granular size is between 1 μ m～5 μ m.Fig. 2 B is CaO and Al 2o 3mass ratio is to amplify the SEM figure that 5.00k obtains at 2: 1, and Fig. 2 C is CaO and Al 2o 3mass ratio is to amplify the SEM figure that 5.00k obtains at 4.5: 1, and Fig. 2 D is CaO and Al 2o 3mass ratio is to amplify the SEM figure that 30k obtains, CaO-Al at 4.5: 1 2o 3catalyst structurally with CaO structural similarity, catalyst granules is piled up and is loosened and have each other larger space, be porous network structure, this porous network structure is beneficial to the turnover of large molecule triglycerides and methanol molecules very much, be fully used in the alkali site of internal pore surface in ester exchange reaction, thereby promoted carrying out fast of reaction.Therefore, this special construction makes the prepared CaO-Al of the present invention 2o 3catalyst has higher catalytic activity.
Catalyst CaO-Al 2o 3the specific area measuring result of (4.5: 1) is as shown in table 2.Compared with the specific area of the CaO making, CaO-Al 2o 3the specific area of catalyst is 15.971m 2.g -1, porosity 0.4311, pore volume 0.045cm 3g -1, aperture 11.28nm, this catalyst has meso-hole structure.Can draw thus CaO-Al 2o 3the reason that catalyst has higher catalytic activity is due to new crystalline phase mayenite Ca on the one hand 12al 14o 33generation, be because specific area is large on the other hand, in unit are, alkali number of loci increases, and greatly improves when using separately CaO to make catalyst thereby make catalytic activity.
Table 2:CaO-Al 2o 3bET result
Fig. 3 is XRD figure (■ CaO, the Ca (OH) of different catalysts of the present invention 2, caCO 3, ca 12al 14o 33), (a), for the XRD spectra of new system CaO gained of the present invention, as shown in Figure 3, be respectively at 2 θ the characteristic peak that CaO appears in 32.2,37.4,53.8,64.1,67.4 and 79.6 places.
(b) be CaO-Al 2o 3mass ratio is the CaO-Al obtaining at 4.5: 1 2o 3the XRD spectra of catalyst, compared with (a), it goes out peak position and peak intensity is all identical with (a), does not have the diffraction maximum of Al or new crystalline phase to occur, and the reason that produces this phenomenon is with Al 2o 3carrier is core, and CaO is successively dispersed in carrier surface, reaches after the threshold value of Monolayer Dispersion, forms multilayer and disperses, thereby make Al 2o 3diffraction maximum suppressed, only have CaO diffraction maximum occur.In addition, make catalyst with independent use CaO compared with, CaO-Al 2o 3(4.5: 1) show stronger catalytic activity, Al in ester exchange reaction 2o 3add the structure that has changed catalyst, this also can draw (seeing Fig. 4) from the asymmetric stretching vibration peak of infrared spectrum Ca-O key weakens.
(c), for CaO uses once without the XRD spectra obtaining after high-temperature calcination, as seen from the figure, use the diffraction maximum of the main component CaO of rear catalyst substantially not have change, be respectively 28.7 ° at 2 θ, 34.1 °, 47.1 °, 50.8 °, and 62.6 ° located to have occurred Ca (OH) 2diffraction maximum, this is owing to there being a small amount of water to cause in system, illustrates that CaO is in use easily disturbed by the moisture in air or in system.
(d), (e) is respectively CaO-Al 2o 3(4.5: 1) are used 1 time, 2 times gained, in figure, all at 20.9 °, 23.3 °, 27.7 °, 29.3 °, 33.3 °, 34.9 °, 36.5 °, 38.2 °, 41.1 °, 46.5 °, 54.9 °, 56.1 °, 57.2 °, locate to occur Ca for 60.5 ° and 71.8 ° 12al 14o 33the diffraction maximum of new crystalline phase mayenite (Mayenite), with freshly prepd CaO-Al 2o 3compare, occur mayenite reason be under hot conditions, CaO and Al 2o 3generation mayenite occurs to interact, but because CaO in preparation is greatly excessive, unnecessary CaO loads on new crystalline phase surface, and after use, certain variation has occurred catalyst structure form, cause and be coated on inner new crystalline phase by CaO and expose and produce diffraction maximum, new crystalline phase jointly plays catalytic action with CaO in Exchange Ester Process, and this tests prepared catalyst in biodiesel synthesis process, and the reaction time is fast, catalytic efficiency is high, and 40～60min yield can reach more than 98%.
(f), (g) is CaO-Al 2o 3after being used 1 time, 20 times, (4.5: 1) calcine 2h gained at 600 DEG C.Compared with (d), (e), in figure, reappear the characteristic peak of CaO, be CaCO 3gained under pyrolytic, Ca 12al 14o 33peak type and peak by force without marked change, and also indifference of the catalytic performance of catalyst, illustrates that catalyst has higher stability.
Fig. 4 is the Different Ca O-Al of new system of the present invention 2o 3the infrared spectrogram of the catalyst of mass ratio.As seen from the figure, 1479cm -1and 1419cm -1near occur be CaO adsorption CO 2after the CO that obtains 3 2-the asymmetric stretching vibration peak of O-C-O key, 874cm -1for CO 3 2-the absworption peak that causes of out-of-plane bending vibration.400～1000cm -1in scope, be the absworption peak of Lattice Oxygen, 779cm -1for the asymmetric stretching vibration peak of Ca-O key.This peak is along with the increase of CaO content, and peak intensity dies down, and works as CaO-Al 2o 3mass ratio is 4.5: 1 o'clock, and the vibration absorption peak of Ca-O key disappears, and Al is described 2o 3add and make lattice structure that variation occur.XRD spectrum in conjunction with Fig. 3 is known, at CaO-Al 2o 3mass ratio is 4.5: 1 o'clock, has Ca 12al 14o 33new crystalline phase generates, and with CaO acting in conjunction, can make catalyst have good activity, conforms to the actual conditions of ester exchange reaction.
4, with CaO-Al 2o 3(4.5: 1) catalysis for preparing biodiesel oil
Utilize purifying waste vegetable oil (with reference to conventional purification process carry out depickling, the processing of coming unstuck, decolour) and methyl alcohol ester exchange reaction prepare biodiesel, reaction condition is: mol ratio 6: 1～12: 1, cosolvent is 5～80wt% n-hexane of waste vegetable oil of purifying or the biodiesel of 5～20wt%, 60～65 DEG C of heating-up temperatures, complex solid base catalyst CaO-Al 2o 31～5wt% of the consumption waste vegetable oil that is purifying, the reaction time is 40～60min.
Concrete operations in the present embodiment: flow chart as shown in Figure 1, the waste vegetable oil of 20.000g purifying is joined in there-necked flask, and add successively 0.600g catalyst, 8.4ml methyl alcohol (9: 1), starts timing after 18.2ml (60wt%) n-hexane or 2.000g biodiesel (10wt%).Centrifugation solid catalyst, rotary evaporation reclaims solvent, and stratification separates lower floor's glycerine, and upper strata is the biodiesel 19.57g of yellow clarification, and productive rate is 97.8%.Adopt gas chromatograph-mass spectrometer (GC-MS) to carry out qualitative and quantitative analysis, the results are shown in Table 3.Obtain the absolute content 99.88% of TFA methyl esters, wherein, 8 kinds of main fatty acid methyl esters account for 95.61% of total amount, be respectively methyl myristate, methyl hexadecanoate, Methyl palmitoleinate, methyl stearate, methyl oleate, methyl linoleate, methyl linolenate and cis-11-eicosenoic acid methyl esters.
Table 3: the GC-MS analysis result of biodiesel fuel component
To catalyst CaO-Al 2o 3(4.5: 1) carry out replica test, and after every secondary response is complete, centrifugation goes out catalyst, and then prepare for biodiesel.Reusable 70 times of catalyst, productive rate keeps more than 98%, as shown in Figure 5.
5, the quality testing of biodiesel
According to the regulation of biodiesel blend fuels (B5) national standard (GB/T 25199-2010), the above-mentioned biodiesel making is detected, the results are shown in Table 4.
Table 4: the quality index of biodiesel
CaO-Al provided by the invention 2o 3the method that complex solid base catalysis waste vegetable oil is prepared biodiesel is ensureing that yield is greater than under 98% prerequisite, the catalysis waste vegetable oil biodiesel reaction time processed shortens to 40～60min, with the equal efficiency of use homogeneous catalyst, respond well, reach the advanced level of domestic and international similar research; And catalyst can be reused and reach 70 times; The present invention uses waste vegetable oil for raw material, cost, and also fast, simple to operate, for promoting New Energy Industry, protection of the environment, significant.
Above embodiment is only in order to technical scheme of the present invention to be described, but not is limited; Although the present invention is had been described in detail with reference to previous embodiment, for the person of ordinary skill of the art, the technical scheme that still can record previous embodiment is modified, or part technical characterictic is wherein equal to replacement; And these amendments or replacement do not make the essence of appropriate technical solution depart from the spirit and scope of the present invention's technical scheme required for protection.

Claims (1)

1. complex solid alkali CaO-Al 2o 3catalyst, is characterized in that: CaO and Al in described catalyst 2o 3mass ratio be 4.5:1, described catalyst is porous network structure, specific area is 15.971 m 2g -1, porosity 0.4311, pore volume 0.045 cm 3g -1, aperture 11.28nm, CaO and Al 2o 3bonding generates new crystalline phase Ca 12al 14o 33,
Described new crystalline phase Ca 12al 14o 33diffraction maximum be 20.9 °, 23.3 °, 27.7 °, 29.3 °, 33.3 °, 34.9 °, 36.5 °, 38.2 °, 41.1 °, 46.5 °, 54.9 °, 56.1 °, 57.2 °, 60.5 ° and 71.8 °;
Described complex solid alkali CaO-Al 2o 3the preparation method of catalyst is polishing, to CaCl 2in solution, add Pidolidone, CaCl 2with the mass ratio of Pidolidone be 200:1 ~ 300:1, stir make it dissolve after, it is slowly joined and CaCl 2the Na of equimolar amounts 2cO 3in solution, suction filtration after 20 ~ 80 DEG C of reaction 1 ~ 6h, respectively with distilled water and ethanol washing 2 ~ 3 times, 100 DEG C of above dry 1 ~ 5 h, get final product to obtain the CaCO of tool Mesoporous Spheres structure 3, by CaCO 3more than 400 DEG C, calcine 1 ~ 4 h, must there is the CaO of Mesoporous Spheres structure;
By the above-mentioned CaCO making 3with Al (OH) 3for 100:19 mixes, be placed in mortar and grind 10 ~ 120min in mass ratio, after fully mixing, in more than 400 DEG C calcining 1 ~ 5 h, the drier that is placed in to be cooled, obtains CaO and Al 2o 3mass ratio is soild alkali catalyst CaO-Al of 4.5:1 2o 3.
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CN101249450A (en) * 2008-03-28 2008-08-27 华东师范大学 Solid body base catalyst and applications for biological diesel oil synthesizing
CN101380570B (en) * 2008-10-24 2010-12-15 吉林大学 Load type solid base catalyst for preparing biology diesel fuel and preparation method thereof

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