CN102744053A - 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 PDFInfo
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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
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 the catalysis waste vegetable oil prepares method of bio-diesel oil.
Background technology
In recent years, the air pollution exhausted day by day and that oil combustion causes of world petroleum resource impels people to seek new alternative energy source.Biodiesel is with vegetable fat, animal fat, their processing or discarded object and microbial grease after using are raw material; Carry out the LCFA mono alkyl ester that ester exchange reaction obtains with low-carbon alcohols, the great attention that the feature of environmental protection that it is outstanding and recyclability cause countries in the world.The U.S., European Union and Japan have taken the lead in producing and the use biodiesel.
Biodiesel does not replace the petrochemical industry oil as yet at present, and reason is that its cost is far above the petrochemical industry oil.According to statistics, the cost of material of biodiesel accounts for 70%～85% of total production cost, and therefore, seeking cheap raw material becomes the matter of utmost importance that reduces the 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 the people with farming; Waste vegetable oil reclaims price lower (being about 3800 yuan/ton) because of it, for 1/2nd of general vegetable oil price, becomes 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 that the most generally adopts in the biodiesel manufacture.Different according to catalyst, 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 than low-k, at this moment grease can be dissolved in methyl alcohol formation single_phase system fully, need not catalyst, and post processing is easy, and the reaction time is 1h; But because the reaction condition of high temperature, high pressure, high to equipment requirements, energy consumption is bigger.The enzymatic transesterification has a lot of advantages, and the reaction time is about 1h, but lipase costs an arm and a leg, and easy inactivation, has hindered it and has been used for the suitability for industrialized production of biodiesel.Adopting homogeneous acid catalysis still is the base catalysis method; Reaction time is generally 30min～60min; The washing but the acid, the base catalyst that have all that catalyst is not easy to separate with product, exist in the product must neutralize; Thereby produce a large amount of sewage, and acid base catalysator can not reuse, bring problems such as higher catalyst cost and acid base catalysator etching apparatus.
In order to solve the separation problem of catalyst and product, the solid base heterogeneous catalytic reaction becomes important research direction.Solid alkali catalytic method has significant advantages such as equipment is simple, post processing is easy, non-environmental-pollution; The reaction time of most solid base heterogeneous catalytic reaction system biodiesel surpasses 1h in the prior art; Can make the reaction time shorten within the 1h only for a few systems 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
To utilizing the solid base heterogeneous catalysis to prepare the defective that the biodiesel cost is high, the catalytic reaction time is long and catalyst can not reuse at present, the object of the present invention is to provide a kind of complex solid alkali CaO-Al
2O
3And the catalysis waste vegetable oil prepares method of bio-diesel oil; The present invention not only provides the novel complex solid base catalyst that can efficiently transform waste vegetable oil; And on the basis of the structure of confirming this catalyst and form and waste vegetable oil purification condition, having optimized with the waste vegetable oil is the process conditions of feedstock production biodiesel; Confirm that influence transforms the key factor of waste vegetable oil, prepare method of bio-diesel oil with waste vegetable oil thereby foundation is quick, low-cost.
For realizing the foregoing invention purpose, 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 the said catalyst
2O
3Mass ratio be optimized for 4.5: 1, said 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
Said 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 of catalysts method, one of said preparation method is a polishing, to CaCl
2Add L-glutamic acid, CaCl in the solution
2With the mass ratio of L-glutamic acid be 200: 1～300: 1, stir make it dissolving after, it is slowly joined and CaCl
2The Na of equimolar amounts
2CO
3In the solution, suction filtration behind 20～80 ℃ of reaction 1～6h is used distilled water and washing with alcohol 2～3 times respectively, drying 1～5h more than 100 ℃, get final product the CaCO of the mesoporous spherical structure of tool
3, with CaCO
3Calcine 1～4h more than 400 ℃, must have the CaO of mesoporous spherical structure;
With the above-mentioned CaCO that makes
3With Al (OH)
3By mass ratio is mixing in 100: 19, places mortar to grind 10～120min, fully mixes the back in calcining 1～5h more than 400 ℃, and the drier that places to be cooled gets CaO and Al
2O
3Mass ratio is 4.5: 1 solid base catalyst CaO-Al
2O
3
The present invention also provides described complex solid alkali CaO-Al
2O
3The Preparation of catalysts method, said preparation method's two is a coprecipitation, with Al (NO
3)
39H
2O and CaCl
2By mass ratio be mix and dissolve at 0.82: 1 calcium aluminium mixed liquor, take by weighing mass ratio and be 7.24: 1 Na
2CO
3And NaOH, add distilled water and make it to dissolve fully, slowly splash in the said calcium aluminium mixed liquor with separatory funnel, stir, in 20～100 ℃ of following ageing 1～12h, suction filtration, 1～5h drier that places to be cooled is calcined in washing more than 400 ℃, get CaO and Al
2O
3Mass ratio is 4.5: 1 solid base catalyst CaO-Al
2O
3
The present invention also provides with complex solid alkali CaO-Al
2O
3The catalysis waste vegetable oil prepares method of bio-diesel oil, and the discarded plant molar equivalent of low-carbon alcohols and purifying 6: 1～12: 1, cosolvent was 5～80wt% of the waste vegetable oil of purifying, 60～65 ℃ of heating-up temperatures, complex solid base catalyst CaO-Al
2O
3Consumption be 1～5wt% of the waste vegetable oil of purifying, the reaction time is 40～60min, the centrifugation solid catalyst, rotary evaporation reclaims solvent, standing demix separates lower floor's glycerine, the upper strata is biodiesel.
Further improvement to technique scheme: it is characterized in that said low-carbon alcohols is a methyl alcohol.
Further improvement to technique scheme: said cosolvent is the biodiesel of n-hexane or the 5～20wt% of 5～80wt%.
Further improvement to technique scheme: said 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
3The catalysis waste vegetable oil prepares method of bio-diesel oil, and under guaranteeing that yield is greater than 98% prerequisite, the reaction time of preparation biodiesel shortens to 40～60min, with the equal efficient of use homogeneous catalyst.
2, reusable.Catalyst of the present invention need not Regeneration Treatment, and is reusable more than 70 times.
3, stable.The compound base catalyst that the present invention synthesized has catalytic activity height, good characteristics of serviceability repeatedly, and catalyst is under reusable situation, and biodiesel production rate is all more than 98%.
4, cost is low.The present invention uses waste vegetable oil to be raw material, and cost reduces greatly, and fast, simple to operate, for promoting new forms of energy industry development, protection environment, significant.
After the advantages specific embodiment of the present invention, other characteristics of the present invention and advantage will become clearer.
Description of 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
31 not calcining is used in (4.5: 1); (e) CaO-Al
2O
32 not calcinings are used in (4.5: 1); (f) CaO-Al
2O
3(4.5: 1) are used 600 ℃ of calcining 2h 1 time; (g) CaO-Al
2O
3(4.5: 1) are used 600 ℃ 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 among the present invention
2O
3The number of times graph of a relation is reused in (4.5: 1).
The specific embodiment
Below in conjunction with the accompanying drawing and the specific embodiment technical scheme of the present invention is done further detailed explanation.
1, novel C aCO
3And the preparation of CaO
Measure 500mL 0.100～2.00molL
-1CaCl
2, add 0.500～3.000g L-glutamic acid, stir and make it dissolving, slowly join 500mL 0.100～2.00molL
-1Na
2CO
3In, suction filtration behind 20～80 ℃ of reaction 1～6h is used distilled water and washing with alcohol 2～3 times respectively, and drying is several hours more than 100 ℃, gets final product to such an extent that the CaCO of special mesoporous spherical structure arranged
3With CaCO
3Calcine 1～4h more than 400 ℃, must have the CaO of analog structure.
2, solid base catalyst CaO-Al
2O
3Preparation
(1) polishing: with the Al (OH) of 1.529g
3Respectively with the above-mentioned CaCO that makes
30.396g, 1.786g, 3.571g, 5.358g, 7.144g, 8.037g, 8.930g mix, and places mortar to grind 10～120min, fully mixes the back in calcining 1～5h more than 400 ℃, the drier that places to be cooled, CaO and Al
2O
3Mass ratio is respectively 1: 4.5,1: 1,2: 1,3: 1,4: 1,4.5: 1,5: 1 CaO-Al
2O
3Solid base catalyst.
(2) coprecipitation: with a certain proportion of CaCl
2And Al (NO
3)
39H
2O mixes and dissolving, takes by weighing the NaOH and the Na of respective quality
2CO
3, add distilled water and make it to dissolve fully, slowly splash in the above-mentioned calcium aluminium mixed liquor with separatory funnel, stir, in 20～100 ℃ of following ageing 1～12h, suction filtration, washing.Calcine 1～5h drier that places to be cooled more than 400 ℃, get CaO and Al
2O
3Mass ratio is respectively 1: 4.5,1: 1,4.5: 1 CaO-Al
2O
3Solid base catalyst.The reagent weighing data is seen table 1.
Table 1: coprecipitation prepares CaO-Al
2O
3Each reagent weighing table of solid base catalyst
3, CaO-Al
2O
3The sign of solid base catalyst
CaO-Al
2O
3The morphology analysis of solid base catalyst is seen Fig. 2, Fig. 3 and Fig. 4.Observe the surperficial form of different catalysts through ESEM (SEM), the result sees Fig. 2.Fig. 2 A is that the above-mentioned CaO that makes 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 SEM figure that 5.00k obtain at 2: 1, and Fig. 2 C is CaO and Al
2O
3Mass ratio is to amplify SEM figure that 5.00k obtain 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 the CaO structural similarity; Catalyst granules is piled up loose and bigger space is arranged each other; Be porous network structure; This porous network structure is beneficial to the turnover of big molecule triglycerides and methanol molecules very much, is fully used in ester exchange reaction in the alkali site of internal pore surface, thereby has promoted carrying out fast of reaction.Therefore, this special construction makes the CaO-Al that the present invention is prepared
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.Compare CaO-Al with the specific area of the CaO that makes
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 CaO-Al thus
2O
3The reason that catalyst has higher catalytic activity is because new crystalline phase mayenite Ca on the one hand
12Al
14O
33Generation, be because specific area is big, and the alkali number of loci increases on the unit are on the other hand, improve greatly 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), as shown in Figure 3 (a) for the XRD spectra of new system CaO gained of the present invention, be respectively the characteristic peak that CaO appears in 32.2,37.4,53.8,64.1,67.4 and 79.6 places at 2 θ.
(b) be CaO-Al
2O
3Mass ratio is 4.5: 1 CaO-Al that obtain
2O
3The XRD spectra of catalyst is compared with (a), and it goes out the 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 a core, and CaO successively is dispersed in carrier surface, reach the threshold value that individual layer disperses after, form multilayer and disperse, thereby make Al
2O
3Diffraction maximum be suppressed, have only the diffraction maximum of CaO to occur.In addition, make catalyst with independent use CaO and compare CaO-Al
2O
3(4.5: 1) show stronger catalytic activity, Al in ester exchange reaction
2O
3Adding changed the structure of catalyst, this draws (see figure 4) also can weakening from the asymmetric stretching vibration peak of infrared spectrum Ca-O key.
(c) for CaO uses once without the XRD spectra that obtains after the high-temperature calcination, can know, use the diffraction maximum of the main component CaO of rear catalyst not have change basically, be respectively 28.7 °, 34.1 °, 47.1 °, locate to have occurred Ca (OH) for 50.8 ° and 62.6 ° at 2 θ by figure
2Diffraction maximum, this is owing to there being a spot of water to cause in the system, explain CaO in use be prone to by in the air or the moisture in the system disturb.
(d), (e) is respectively CaO-Al
2O
31 time, 2 times gained are used in (4.5: 1), 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 ° among the figure
12Al
14O
33The diffraction maximum of new crystalline phase mayenite (Mayenite) is with freshly prepd CaO-Al
2O
3Compare, occur mayenite reason be under hot conditions, CaO and Al
2O
3Taking place to interact generates mayenite, yet owing to CaO in preparation is excessive greatly, unnecessary CaO loads on new crystalline phase surface; After the use, certain variation has taken place in the catalyst structure form, causes by CaO to be coated on inner new crystalline phase exposure and to produce diffraction maximum; New crystalline phase plays catalytic action with CaO jointly in the ester exchange process, the prepared catalyst of this experiment is in the 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 using 1 time, 20 times, (4.5: 1) calcine the 2h gained at 600 ℃.Compare with (d), (e), reappeared the characteristic peak of CaO among the figure, be CaCO
3Gained under pyrolytic, Ca
12Al
14O
33Peak type and peak do not have marked change by force, and also indifference of the catalytic performance of catalyst explains that catalyst has advantages of 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.Visible by figure, 1479cm
-1And 1419cm
-1Near that occur is CaO surface adsorption CO
2After the CO that obtains
3 2-The asymmetric stretching vibration peak of O-C-O key, 874cm
-1Be CO
3 2-The absworption peak that causes of out-of-plane bending vibration.400～1000cm
-1Then the absworption peak of Lattice Oxygen in the scope, 779cm
-1Asymmetric stretching vibration peak for the 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
3Adding make lattice structure that variation take place.XRD spectrum in conjunction with Fig. 3 can be known, at CaO-Al
2O
3Mass ratio is 4.5: 1 o'clock, and Ca is arranged
12Al
14O
33New crystalline phase generates, and with the CaO acting in conjunction, can make catalyst have good active, 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 the methyl alcohol ester exchange reaction prepare biodiesel; Reaction condition is: mol ratio 6: 1～12: 1; Cosolvent is 5～80wt% n-hexane or the biodiesel of 5～20wt% of the waste vegetable oil of purifying; 60～65 ℃ of heating-up temperatures, complex solid base catalyst CaO-Al
2O
3Consumption be 1～5wt% of the waste vegetable oil of 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 the there-necked flask; And adding the 0.600g catalyst successively, 8.4ml methyl alcohol (9: 1) picks up counting after 18.2ml (60wt%) n-hexane or the 2.000g biodiesel (10wt%).The centrifugation solid catalyst, rotary evaporation reclaims solvent, and standing demix separates lower floor's glycerine, and the 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 result sees 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 suitable-11-eicosenoic acid methyl esters.
Table 3: the GC-MS analysis result of biodiesel fuel component
To catalyst CaO-Al
2O
3Replica test is carried out in (4.5: 1), after having reacted at every turn, centrifugalizes out catalyst, and then is used for biodiesel manufacture.Reusable 70 times of catalyst, productive rate keep more than 98%, and be as shown in Figure 5.
5, the quality testing of biodiesel
Regulation according to biodiesel blending fuel (B5) national standard (GB/T 25199-2010) detects the above-mentioned biodiesel that makes, and the result sees table 4.
Table 4: the quality index of biodiesel
CaO-Al provided by the invention
2O
3Complex solid base catalysis waste vegetable oil prepares method of bio-diesel oil under guaranteeing that yield is greater than 98% prerequisite; The catalysis waste vegetable oil system biodiesel reaction time shortens to 40～60min; With the equal efficient 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 to be raw material, and cost reduces, and fast, simple to operate, for promoting new forms of energy industry development, protection environment, significant.
Above embodiment is only in order to explaining technical scheme of the present invention, but not limits it; Although the present invention has been carried out detailed explanation with reference to previous embodiment, for the person of ordinary skill of the art, still can make amendment to the technical scheme that previous embodiment is put down in writing, perhaps part technical characterictic wherein is equal to replacement; And these modifications or replacement do not make the essence of relevant art scheme break away from the spirit and the scope of the present invention's technical scheme required for protection.
Claims (8)
1. complex solid alkali CaO-Al
2O
3Catalyst is characterized in that: CaO and Al in the said catalyst
2O
3Mass ratio be optimized for 4.5:1, said 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
2. complex solid alkali CaO-Al according to claim 1
2O
3Catalyst is characterized in that said 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 °.
3. complex solid alkali CaO-Al according to claim 1
2O
3The Preparation of catalysts method is characterized in that: said preparation method is a polishing, to CaCl
2Add L-glutamic acid, CaCl in the solution
2With the mass ratio of L-glutamic acid be 200:1 ~ 300:1, stir make it dissolving after, it is slowly joined and CaCl
2The Na of equimolar amounts
2CO
3In the solution, suction filtration behind 20 ~ 80 ℃ of reaction 1 ~ 6h is used distilled water and washing with alcohol 2 ~ 3 times respectively, drying 1 ~ 5 h more than 100 ℃, get final product the CaCO of the mesoporous spherical structure of tool
3, with CaCO
3Calcine 1 ~ 4 h more than 400 ℃, must have the CaO of mesoporous spherical structure;
With the above-mentioned CaCO that makes
3With Al (OH)
3By mass ratio is that 100:19 mixes, and places mortar to grind 10 ~ 120min, fully mixes the back in calcining 1 ~ 5 h more than 400 ℃, and the drier that places to be cooled gets CaO and Al
2O
3Mass ratio is the solid base catalyst CaO-Al of 4.5:1
2O
3
4. complex solid alkali CaO-Al according to claim 1
2O
3The Preparation of catalysts method is characterized in that: said preparation method is a coprecipitation, with Al (NO
3)
39H
2O and CaCl
2By mass ratio be 0.82:1 mix and dissolve calcium aluminium mixed liquor, add excessive N a
2CO
3And NaOH, the two mass ratio is 7.24: 1, adds distilled water and makes it to dissolve fully, slowly splashes in the said calcium aluminium mixed liquor with separatory funnel; Stir, in 20 ~ 100 ℃ of following ageing 1 ~ 12h, suction filtration; 1 ~ 5h drier that places to be cooled is calcined in washing more than 400 ℃, get CaO and Al
2O
3Mass ratio is the solid base catalyst CaO-Al of 4.5:1
2O
3
5. with complex solid alkali CaO-Al
2O
3The catalysis waste vegetable oil prepares method of bio-diesel oil; It is characterized in that: at the discarded plant molar equivalent 6:1 ~ 12:1 of low-carbon alcohols and purifying; Cosolvent is 5 ~ 80 wt % of the waste vegetable oil of purifying, 60 ~ 65 ℃ of heating-up temperatures, complex solid base catalyst CaO-Al
2O
3Consumption be 1 ~ 5wt % of the waste vegetable oil of purifying, the reaction time is 40 ~ 60min, the centrifugation solid catalyst, rotary evaporation reclaims solvent, standing demix separates lower floor's glycerine, the upper strata is biodiesel.
6. according to claim 5 with complex solid alkali CaO-Al
2O
3The catalysis waste vegetable oil prepares method of bio-diesel oil, it is characterized in that said low-carbon alcohols is a methyl alcohol.
7. according to claim 5 with complex solid alkali CaO-Al
2O
3The catalysis waste vegetable oil prepares method of bio-diesel oil, it is characterized in that said cosolvent is the biodiesel of n-hexane or 5 ~ 20 wt % of 5 ~ 80 wt %.
8. according to claim 5 with complex solid alkali CaO-Al
2O
3The catalysis waste vegetable oil prepares method of bio-diesel oil, it is characterized in that said catalyst CaO-Al
2O
3Reuse more than 70 times, productive rate reaches more than 98%.
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| CN106391075A (en) * | 2016-08-31 | 2017-02-15 | 乐山纯新能源科技有限公司 | High-efficiency bio-diesel catalyst |
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| CN109876790A (en) * | 2019-01-02 | 2019-06-14 | 湘潭大学 | A kind of CaO-MgO-Al2O3The method of catalyzed by solid base biodiesel synthesis |
| CN113509946A (en) * | 2020-04-10 | 2021-10-19 | 中石化南京化工研究院有限公司 | Supported alumina solid base catalyst |
| CN112156783A (en) * | 2020-09-07 | 2021-01-01 | 广州大学 | Ni-CaO-Ca12Al14O33Preparation method and application of bifunctional catalyst |
| CN112156783B (en) * | 2020-09-07 | 2023-02-28 | 广州大学 | Ni-CaO-Ca 12 Al 14 O 33 Preparation method and application of bifunctional catalyst |
| TWI806375B (en) * | 2022-01-21 | 2023-06-21 | 國立清華大學 | Manufacturing method of glycidol |
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